Reviews

Published on May 2016 | Categories: Documents | Downloads: 50 | Comments: 0 | Views: 1623
of 287
Download PDF   Embed   Report

Comments

Content

1
Reaction Intermediates in Organic Chemistry: the "Big Picture"
John Andraos
Department of Chemistry, York University, Toronto, ON M3J 1P3
[email protected]
FAX: 416-736-5936
Supplementary Material
Table S5. Table summarizing reactions that lead to the suggestion, discovery, and identification of various reaction intermediates
Acylium ions (oxocarbonium ions)
+
+
R

C

O

R

C

O

Reviews:
Olah, G.A.; Germain, A.; White, A.M. in Carbonium Ions (G.A. Olah; P.v.R. Schleyer, eds.) Wiley-Interscience: New York, 1976, Vol. 5, p. 2049
- 2133
+O
COOH

C

H2 SO4

HSO4 - + H 2 O

Treffers, H.P.; Hammett, L.P. J. Am. Chem. Soc. 1937, 59, 1708
Burton, H.; Praill, P.F.G. J. Chem. Soc. 1955, 729
Chmiel, C.T.; Long, F.A. J. Am. Chem. Soc. 1956, 78, 3326
Ladenheim, H.; Bender, M.L.. J. Am. Chem. Soc. 1960, 82, 1895
Bender, M.L.; Feng, M.S. J. Am. Chem. Soc. 1960, 82, 6318
Bender, M.L.; Ladenheim, H.; Chen, M.C. J. Am. Chem. Soc. 1961, 83, 123
Yamase, Y. Bull. Chem. Soc. Jpn. 1961, 34, 484
Cook, D. Can. J. Chem. 1961, 40, 445

2

N-Acylonium ions (acylammonium ions)
O

+
R1

R2

N
R3
R4

Reviews:
Beckwith, A.L.J. in The Chemistry of Amides (Zabicky, J.; ed.) Wiley-Interscience: New York, 1970, Chapter 2, p. 77-81
Kröhnke, F.; Heffe, W. Chem. Ber. 1937, 70B, 1720
Prey, A. Chem. Ber. 1942, 75, 537
Adkins, H.; Thompson, Q.E. J. Am. Chem. Soc. 1949, 71, 2242
Klages, F.; Zange, E. Ann. Chem. 1957, 607, 35
Cook, D. Can. J. Chem. 1962, 40, 2362
Alleneoxide
O
R1
R3

R2
R4

Reviews:
Chan, T.H.; Ong, B.S. Tetrahedron 1980, 36, 2269

3

tBu

O

tBu

mCPBA
H

tBu

tBu

H

H

Camp, R.L.; Greene, F.D. J. Am. Chem. Soc. 1968, 90, 7349
O

CH3 (CO)OOH

O

+

OH

OAc

27%

64%
Crandall, J.K.; Paulson, D.R.; Bunnell, C.A. Tetrahedron Lett. 1968, 5063
O

O

O

OAc

OH

HOOAc
O
O

HO

Crandall, J.K.; Machleder, W.H. J. Am. Chem. Soc. 1968, 90, 7292
Aromatic π-complexes

OAc

O

O

4

X

Reviews:
Stock, L.M. Adv. Phys. Org. Chem. 1963, 1, 35
Berliner, E. Prog. Phys. Org. Chem. 1964, 2, 253
Baciocchi, E.; Illuminati, G. Prog. Phys. Org. Chem. 1967, 5, 1
Olah, G.A. Acc. Chem. Res. 1971, 4, 240
Lenoir, D. Angew. Chem. Int. Ed. 2003, 42, 854
(i) Charge transfer complexes
Reviews:
Dewar, M.J.S. Electronic Theory of Organic Chemistry, Oxford University Press: New York, 1949
Kosower, E.M. Prog. Phys. Org. Chem. 1965, 3, 81
Blatchly, J.M. Educ. Chem. 1970, 7, 62
Ruasse, F. Adv. Phys. Org. Chem. 1993, 28, 207
NH2

NH2

NH

+ NH2

HN

NH

+

+
H

H

Dewar, M.J.S. Nature 1945, 156, 784 (first suggestion)
Dewar, M.J.S. J. Chem. Soc. 1946, 406; 777

5
CH3

CH3

HAlCl4

H+ AlCl4 -

Brown, H.C.; Brady, J.D. J. Am. Chem. Soc. 1952, 74, 3570
Br
Al

Br

AlBr3

Br

Brown, H.C.; Wallace, W.J. J. Am. Chem. Soc. 1953, 75, 6265
O
+N
-O

ON+
O

Addison, C.C. Rec. Trav. Chim. Pays-Bas 1956, 75, 626
OH
O2N

NO2

Ar

NO2

Kross, R.D.; Fassel, V.A. J. Am. Chem. Soc. 1957, 79, 38

6
R
R2

CHCl3

CHCl3
R1

Reeves, L.W.; Schneider, W.G. Can. J. Chem. 1957, 35, 251
(proton NMR signal of chloroform as function of concentration of aromatic or olefinic compound)
Brown, H.C.; Stock, L.M. J. Am. Chem. Soc. 1957, 79, 1421
R2
R1

NC

CN

R1 = H, R2 = H
R1 = H, R2 = CH 3

NC

CN

R1 = CH 3 , R 2 = CH 3

Merrifield, R.E.; Phillips, W.D. J. Am. Chem. Soc. 1958, 80, 2778
Cairns, T.L.; Carboni, R.A.; Coffman, D.D.; Engelhardt, V.A.; Heckert, R.E.; Little, E.L.; McGeer, E.G.; McKusik, B.C.; Middleton, W.J.;
Scribner, R.M.; Theobold, C.W.; Windberg, H.E. J. Am. Chem. Soc. 1958, 80, 2775

CO

+ W(CO)6

OC

- 2 CO OC

W

Me6

W(CO)3

- CO
CO

Manuel, T.A.; Stone, F.G.A. Chem. Ind. 1959, 1349

Me6

7
R

HX X = Cl, Br

Brown, H.C.; Melchiore, J.J. J. Am. Chem. Soc. 1965, 87, 5269
O

O2N

NO2

Ar

NO2

Schenk, G.H.; Vance, P.W.; Pietrandrea, J.; Mojzis, C. Anal. Chem. 1965, 37, 372
(ii) "Sandwich" complexes (metallocenes)
Reviews:
Jutzi, P. Pure Appl Chem. 1989, 61, 1731
Grebenik, P.; Grinter, R.; Perutz, R.N. Chem. Soc. Rev. 1988, 17, 453
Jonas, K. Pure Appl. Chem. 1984, 56, 63
Schloegel, K. Pure Appl. Chem. 1970, 23, 413
Schloegel, K. Top. Stereochem. 1967, 1, 39
Hein, F. Chem. Ber. 1919, 52, 195

8
H

MgBr

Mg
EtBr

EtMgBr
- EtH

H

_

MgBr

H

3

2 FeCl3
- 3 MgBrCl
- FeCl2

Fe +2

Cl

+

_

Kealy, T.J.; Pauson, P.L. Nature 1951, 168, 1039
Wilkinson, G.; Rosenblum, M.; Whiting, M.C.; Woodward, R.B. J. Am. Chem. Soc. 1952, 74, 2125
Woodward, R.B.; Rosenblum, M.; Whiting, M.C. J. Am. Chem. Soc. 1952, 74, 3458
Eiland, P.F.; Pepinsky, R. J. Am. Chem. Soc. 1952, 74, 4971
Wilkinson, G. J. Am. Chem. Soc. 1954, 76, 209
MXn + n AlCl3 + 2 Me6 C6

[MC6 Me6 ]+n [AlX4 -]n

M = Co, Rh; X = Cl, Br
Fischer, E.O.; Lindner, H.H. J. Organometallic Chem. 1964, 1, 307
Aromatic σ-complexes (see Meisenheimer-Jackson complexes and Janovsky complexes for negatively charged complexes;
Wheland intermediates for positively charged complexes)

9
R1

R1

+

R6

R2

R1

R6

R2

R6

R2

+
R5

R3
E

+

R5

R4

R3
E

R5

R4

R3
E

R4

Reaction with electrophiles, E+
R1

Nu

R6

_

R1
R2

R1

Nu

R6

R2

R6

R3

R5

Nu
R2

_

_
R5

R3
R4

R5
R4

R3
R4

Reaction with nucleophiles, NuReviews:
Ross, S.D. Prog. Phys. Org. Chem. 1963, 1, 31
Stock, L.M. Adv. Phys. Org. Chem. 1963, 1, 35
Berliner, E. Prog. Phys. Org. Chem. 1964, 2, 253
Baciocchi, E.; Illuminati, G. Prog. Phys. Org. Chem. 1967, 5, 1
Buncel, E.; Norris, A.R.; Russell, K.E. Quart. Rev. Chem. Soc. 1968, 22, 123
Olah, G.A. Acc. Chem. Res. 1971, 4, 240

10

+ HF + BF3

BF4 -

+

H

H

Kilpatrick, M.; Luborsky, F.E. J. Am. Chem. Soc. 1953, 75, 577
Olah, G.A.; Kuhn, S.J.; Pavlath, A. Nature 1956, 178, 693
Olah, G.A.; Kuhn, S.J.; Pavlath, A. J. Am. Chem. Soc. 1958, 80, 6535; 6541
Doering, W.v.E.; Saunders, M.; Boyton, H.G.; Earhart, H.W.; Wadley, E.F.; Edwards, W.R.; Laber, R. Tetrahedron 1958, 4, 178
Arylium ions (see phenyl cation)
Aziridinium ions
R

R
N+

R1

R2

Reviews:
Crist, D.R.; Leonard, N.J. Angew. Chem. Int. Ed. 1969, 8, 962

11

N
Cl

Cl

- Cl-

N+

Cl

H2 O
-H

+

N
HO

Cl

- ClH2 O

N
HO

OH

OH
N+

- H+

Golumbic, C.; Fruton, J.S.; Bergmann, M. J. Org. Chem. 1946, 11, 518
Fruton, J.S.; Bergmann, M. J. Org. Chem. 1946, 11, 543
Golumbic, C.; Stahlmann, M.A.; Bergmann, M. J. Org. Chem. 1946, 11, 550
R

R

R

N

N+
Cl

Cl
R

Cl-

R
N
R

Kerwin, J.F.; Ullyot, G.E.; Fuson, R.C.; Zirkle, C.L. J. Am. Chem. Soc. 1947, 69, 2961
Hanby, W.E.; Hartley, G.S.; Powell, E.O.; Rydon, H.N. J. Chem. Soc. Abstr. 1947, 519
Schultz, E.M.; Sprague, J.M. J. Am. Chem. Soc. 1948, 70, 48
Fuson, R.C.; Zirkle, C.L. J. Am. Chem. Soc. 1948, 70, 2760
Freundlich, H.; Salomon, G. Z. Physik. Chem. 1933, 166A, 161
Bartlett, P.D.; Ross, S.D.; Swain, C.G. J. Am. Chem. Soc. 1947, 69, 2971
Benzyne (arynes)

Reviews:
Fields, E.K.; Meyerson, S. Adv. Phys. Org. Chem. 1968, 6, 1

12
Gilcrist, T.L.; Rees, C.W. Carbenes, Nitrenes, and Arynes, Appleton-Century Crofts: New York, 1969
Fields, E.K. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 449
Brown, R.F.C. Eur. J. Org. Chem. 1999, 3211
Sander, W. Acc. Chem. Res. 1999, 32, 669 (m-benzyne and p-benzyne)
Pellissier, H.; Santelli, M. Tetrahedron 2003, 59, 701 (arynes in syntheses)

pyrolysis

CH4 +

+ other products

Berthelot, A. Compt. Rend. 1866, 63, 790
Berthelot, A. Ann. Chem. 1867, 142, 254
Berthelot, A. Bull. Soc. Chim. Fr. 1867, 7[2], 218
Badger, G.M.; Spotswood, T.M. J. Chem. Soc. 1960, 4420
SO3 R

OH

NaOH

+ RSO3 Na + H 2 O


Kekule, A. Compt. Rend. 1864, 64, 753
Cl

NaOH
RO3S
RO3S


Cl

HO

- RSO3 Na
- H2 O

Limpricht, H. Chem. Ber. 1874, 7, 1439

OH

13

Br

CH3

NH

NaOH

+ 2

NH

- 2 HBr
Br

NH2

Kym, O. J. Prakt. Chem. 1895, 51[2], 325
Cl

Cl
Cl

Cl

2 Ph2 N- K+

Ph2 N

NPh2

+ 2 KCl

Cl

Cl

Haeussermann, C. Chem. Ber. 1900, 33, 939
Haeussermann, C. Chem. Ber. 1901, 34, 38
Br

KOH / EtOH

EtOH
OEt

- HBr
O

O

O

14
Stoermer, R.; Kahlert, B. Chem. Ber. 1902, 35, 1633 (first suggestion of existence of triple bond in small ring compounds)
Cl
Cl

Cl

300 C

Ph-Cl
+

- HCl
Meyer, K.H.; Bergius, F. Chem. Ber. 1914, 47, 3159
Bachmann, W.E.; Clarke, H.T. J. Am. Chem. Soc. 1927, 49, 2089 (first suggestion of existence of benzyne)
Lüttringhaus, A.; Saaf, G. Ann. Chem. 1930, 542, 250 (aryl-phenol rearrangement)
Cl

*

NH2

*

*

+ KNH2

*

- KCl
NH2

50%

50%

Roberts, J.D.; Simmons, H.E. Jr.; Carlsmith, L.A.; Vaughan, W.C. J. Am. Chem. Soc. 1953, 75, 3290
Roberts, J.D.; Semenov, D.A.; Simmons, H.E. Jr.; Carlsmith, L.A. J. Am. Chem. Soc. 1956, 78, 601
Roberts, J.D.; Vaughan, C.W. Jr.; Carlsmith, L.A.; Semenov, D.A. J. Am. Chem. Soc. 1956, 78, 611
Scardiglia, F.; Roberts, J.D. Tetrahedron 1957, 1, 343
Bottini, A.T.; Roberts, J.D. J. Am. Chem. Soc. 1957, 79, 1458
F

Li

F

Ph-Li

Ph-Li
- Ph-H

- LiF
Li

Wittig, G.; Fuhrmann, G. Chem. Ber. 1940, 73, 1197

Ph

15
OH

O
Br

Li

Li(Hg)

H+
O

- LiF
F

F

H2 / Pd
H+
O

Wittig, G. Naturwiss. 1942, 30, 696
Wittig, G.; Harborth, G. Chem. Ber. 1944, 77, 306; 316
Wittig, G.; Pohmer, L. Angew. Chem. 1955, 67, 348
Wittig, G.; Pohmer, L. Chem. Ber. 1956, 89, 1334
Wittig, G. Pure Appl. Chem. 1963, 7, 173
F
Ph (COOH)

Ph-Li
F

- Ph-H
- LiF

Huisgen, R.; Rist, H. Naturwiss. 1954, 41, 358
Huisgen, R.; Rist, H. Ann. Chem. 1955, 594, 137

Ph-Li
CO2

COOH (Ph)

16
Huisgen, R.; Knorr, R. Tetrahedron Lett. 1963, 1017
Levine, R.; Leake, W.W. Science 1955, 121, 780
Müller, E.; Roscheisen, G. Chem. Ztg. 1956, 80, 101
Cl

RNa

R

R = amyl

Morton, A.A.; Davidson, J.B.; Hakan, B.L. J. Am. Chem. Soc. 1942, 64, 2242
Morton, A.A. J. Org. Chem. 1956, 21, 593
Heaney, H.; Mann, F.G.; Millar, I.T. J. Chem. Soc. 1957, 3930

17
O

O

FVP
O

- CO

..

O

O

O

O

O

O

- CO

O

.
.
- CO

O

benzyne
O

O

O

+
O

- CO
benzyne
O

Brown, R.F.C.; Solly, R.K. Austr. J. Chem. 1966, 19, 1045
O
N
O

O


Ar / 10 K
- CO
- CO2

N

18
Nam, H.H.; Leroi, G.E. J. Am. Chem. Soc. 1988, 110, 4096 (first observation of 3,4-pyridyne)
Betaines (phosphonium betaines)
+
-O

PR3

R1

R4
R2

R3

Reviews:
Wittig, G. Pure Appl. Chem. 1964, 9, 245
Vedejs, E. Science 1980, 207, 42
Wittig, G. Science 1980, 210, 600
Br

+

+
+ PPh 3

PPh3

nBuLi

Br-

- nBuH
- LiBr

PPh3

_
ylide

+
O

+
PPh3

_

-O

PPh3

PhLi

PPh3

_

+
R

H

- PhH
R

R

betaine
Wittig, G.; Schöllkopf, U., Chem. Ber. 1954, 87, 1318
Wittig, G.; Haag, W. Chem. Ber. 1955, 88, 1654
Wittig, G.; Pommer, H. DE 32741 BASF (1954)
Biradicals

+
-O

tBuOH
+

Li

- LiOtBu
- O=PPh3

R

19

OH

.

.

O

R3

.

R1

R2

..

.

.

CH2

CH2

.

. .

.

CH2

.

. .

CH2

CH2

CH2

.

.

.

O

O

R1

.

..

C

C

R2

R3

R4

Reviews:
Kuivila, H.G. Acc. Chem. Res. 1968, 1, 299 (organotin hydrides and organic free radicals)
Borden, W.T. (ed.) Diradicals, Wiley: New York, 1982
Platz, M.S. (ed.) Kinetics and Spectroscopy of Carbenes and Biradicals, Plenum Press: New York, 1990
Cramer, J. Chem. Soc. Perkin Trans. 2 1998, 1007 (biradicals - Paul Dowd)
Arnold, B.R.; Bucher, G.; Netto-Ferreira, J.C.; Platz, M.S.; Scaiano, J.C. Biradicals, Radicals in Excited States, Carbenes, and Related Species,
Springer-Verlag: Weinheim, 1998
Sander, W. Acc. Chem. Res. 1999, 32, 669 (m-benzyne and p-benzyne)
Thiele hydrocarbon (biradical)

.

Ph

Ph

.

Ph

Ph

Ph

Ph

Ph

Ph

Thiele, J.; Balhorn, H. Chem. Ber. 1904, 37, 1463
Chichibabin hydrocarbon (biradical)

20

Ph

Ph

.

Ph

Ph

Cl

Ph

Ph

Ph

Ph

Ph

Ph

Na or K

Cl
Ph

.

- NaCl or
KCl

Ph

Chichibabin, A.E. Zh. Russ. Fiz.-Khim., Obshchestva 1907, 39, 925
Chichibabin, A.E. Chem. Ber. 1907, 40, 1810
Schlenk-Brauns hydrocarbon (biradical)
Ph

Ph

Cl

Cl

Ph

Ph

Na or K

Ph

Ph

Ph

.

.

Ph

- NaCl or
KCl
Cl
Ph

Ph

Ph

Cl
Ph Ph

.

Ph

Na or K
- NaCl
or - KCl
Schlenk, W.; Brauns, M. Chem. Ber. 1915, 48, 661; 716

Ph

.

Ph

21
Müller hydrocarbon (biradical)
Cl

Cl

.

.

Ph

Ph

Ph

Ph
Cl

Cl

Müller, E.; Neuhoff, H. Chem. Ber. 1939, 72, 2063
Müller, E.; Tietze, E. Naturwiss. 1940, 28, 189
Müller, E.; Tietze, E. Chem. Ber. 1941, 74, 807
O

O

Ph

Cl

2 PhCOCl
AlCl3

2 PhLi
Ph

Ph

Cl

Cl
Ph

Ph

- CuCl
or AgCl

.

Ph

Ph

Cu or Ag

.

Ph

Ph

Fe
HCl

Ph
HO
Ph

Ph
OH
Ph

22
Müller, E.; Pfanz, H. Chem. Ber. 1941, 74, 1051
Wittig, G.; von Lupin, F. Chem. Ber. 1928, 61B, 1627
Wittig, G.; Leo, M. Chem. Ber. 1929, 62B, 1405
Schönberg, A.; von Vargha, L. Chem. Ber. 1931, 64B, 1390
Wittig, G.; Leo, M. Chem. Ber. 1931, 64B, 2395
Schönberg, A.; Cernik, D.; Urban, W. Chem. Ber. 1931, 64B, 2577
Schönberg, A. Chem. Ber. 1934, 67B, 1404
Dufraisse, C. Chem. Ber. 1934, 67B, 2018
Schönberg, A. Chem. Ber. 1935, 68B, 162
Schönberg, A. Ann. Chem. 1935, 518, 299
Ph

Ph

.

Ph

Ph

.

Ph

Ph

Ph

Ph

paramagnetism of biradicals:
Müller, E. Z. Elektrochem. 1934, 40, 542
Müller, E.; Klemm, W.; Schuth, W. Naturwiss. 1934, 22, 335
Müller, E.; Müller-Rodloff, I. Ann. Chem. 1935, 517, 134
Müller, E.; Müller-Rodloff, I. Chem. Ber. 1935, 68B, 1276
Müller, E.; Müller-Rodloff, I. Ann. Chem. 1936, 521, 81
Müller, E.; Bunge, W. Chem. Ber. 1936, 69, 2164; 2168
Müller, E. Naturwiss. 1937, 25, 545
Müller, E.; Dammerau, I. Chem. Ber. 1937, 70B, 2561
Müller, E.; Sok, G. Chem. Ber. 1937, 70B, 1990
Clar, E. Chem. Ber. 1935, 68B, 2066
Schönberg, A. Trans. Faraday Soc. 1936, 32, 514
Allen, F.L.; Sugden, S. J. Chem. Soc. 1936, 440
Dufraisse, C. J. Am. Chem. Soc. 1936, 58, 858
Hückel, E. Z. Physik. Chem. 1936, B34, 339

23
+ CO
Norrish Type I
O

..



α cleavage

+ CH 2 =CH 2 + CO

O

Hα abstraction

O
C

Hδ abstraction

CHO

+ CO
Norrish Type II
R2

R2

O

O


R1

*3
Hγ abstraction

R1

OH

Bamford, C.H.; Norrish, R.G.W. J. Chem. Soc. 1935, 1504
Norrish, R.G.W.; Bamford, C.H. Nature 1936, 138, 1016
Norrish, R.G.W.; Bamford, C.H. Nature 1937, 140, 195
Norrish, R.G.W. Trans. Faraday Soc. 1937, 33, 1521

R1

Bawn, C.E.H.; Hunter, R.F. Trans. Faraday Soc. 1938, 34, 608
Fuson, R.C.; Lundquist, W.E. J. Am. Chem. Soc. 1938, 60, 1889
Enderlin, L. Ann. Chim. Phys. 1938, 10, 5
Bawn, C.E.H.; Milsted, J. Trans. Faraday Soc. 1939, 35, 889

.

.

R2
OH

β cleavage

R2
+

R1

24


N

N

- N2

.

.


- CO

O

Dowd, P. J. Am. Chem. Soc. 1966, 88, 2587 (first observation of biradicals by ESR)
R3
R1

R1

.

OR
R3

ROH
R2

R2

.

R4

R1

R3

R2

R4

R4

Bergman, R.G.; Jones, R.R., J. Am. Chem. Soc. 1972, 94, 660 (Bergmann cyclization)
CH2

. .
CH2

Pagni, R.; Burnett, M.N.; Dodd, J.R. J. Am. Chem. Soc. 1977, 99, 1972

.

O

CH2

.

25
Rule, M.; Matlin, A.R.; Dougherty, D.A.; Hilinski, E.; Berson, J.A. J. Am. Chem. Soc. 1979, 101, 5098
*3
O

O

O



CH2 =CH 2

. .

O

Freilich, S.F.; Peters, K.S. J. Am. Chem. Soc. 1981, 103, 6255; 1985, 107, 3819 (evidence for biradical in Paterno-Büchi reaction)
Bridged carbocations (see halonium ions, non-classical ions, and phenonium ions)

+

Nevell, T.P.; de Salas, E.; Wilson, C.L. J. Chem. Soc. 1939, 1188 (first suggestion)

:

Carbanions
_
R1

C

R3

R2

Reviews:
Szwarc, M. (ed.) Carbanions: living polymers and electron transfer processes, Wiley: New York, 1968
Kaiser, E.M.; Slocum, D.W. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 337
Hogen-Esch, T.E. Adv. Phys. Org. Chem. 1977, 15, 154
Stowell, J.C. Carbanions in Organic Synthesis, Wiley: New York, 1979
Buncel, E.; Durst, T. (eds.) Comprehensive Carbanion Chemistry, Part A: structure and reactivity, Elsevier: Amsterdam, 1980
Gau, G.; Assadourian, L.; Veracini, S. Prog. Phys. Org. Chem. 1987, 16, 237
Nibbering, N.M.M. Adv. Phys. Org. Chem. 1988, 24, 1

26
Harder, S. Chem. Eur. J. 2002, 8, 3229
Buncel, E.; Dust, J.M. Carbanion Chemistry: structures and mechanisms, Oxford University Press: Oxford, 2003
stabilities of carbanions:
Breslow, R.; Balasubramanian, K. J. Am. Chem. Soc. 1969, 91, 5182 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Chu, W. J. Am. Chem. Soc. 1970, 92, 2165 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Chu, W. J. Am. Chem. Soc. 1973, 95, 411 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Mazur, M. J. Am. Chem. Soc. 1973, 95, 584 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Drury, R.F. J. Am. Chem. Soc. 1974, 96, 4702 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R. Pure Appl. Chem. 1974, 40, 493 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Wasielewski, M.R.; Breslow, R. J. Am. Chem. Soc. 1976, 98, 4222 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Goodin, R. J. Am. Chem. Soc. 1976, 98, 6077 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Bank, S.; Ehrlich, C.L.; Zubieta, J.A. J. Org. Chem. 1979, 44, 1454 (trityl carbanions)
Bank, S.; Ehrlich, C.L.; Mazur, M.; Zubieta, J.A. J. Org. Chem. 1981, 46, 1243 (trityl carbanions)
organomagnesium compounds
Hallwachs, W.; Schafarik, F. Ann. Chem. 1859, 109, 206
Cahours, A. Ann. Chem. 1859, 114, 227
Grignard, V. Ann. Chim. Phys. 1901, 24, 433
Zincke, T.; Suhl, R.S. Chem. Ber. 1907, 39, 4148
Fromberz, K.; Meigen, W. Chem. Ber. 1907, 40, 403
Schiff, H. Ann. Chem. 1907, 352, 73
Ph

Ph

+
NMe4

_
Ph

Ph

+
NMe4

_
H

H

Schlenk, W. Ann. Chem. 1910, 372, 1
Wren, H. J. Chem. Soc. 1910, 95, 1583
Wren, H. J. Chem. Soc. 1910, 95, 1593
Tarbouriech, P.J. Compt. Rend. 1910, 149, 862
Freylon, G. Ann. Chim. Phys. 1910, 19, 551

27
Mitchell, A.D.; Thorpe, J.F. Proc. Chem. Soc. 1911, 26, 248
Mitchell, A.D.; Thorpe, J.F. Proc. Chem. Soc. 1911, 26, 2261
Dieckmann, W. Chem. Ber. 1911, 44, 981
Busch, M.; Limpach, O. Chem. Ber. 1911, 44, 1573
Locquin, R. Compt. Rend. 1911, 153, 284
Curtius, T. Chem. Ztg. 1912, 35, 249
Tarbouriech, P.J. Compt. Rend. 1913, 156, 75
Wislicenus, W.; Elvert, H.R.; Kurtz, P. Chem. Ber. 1914, 46, 3395
Curtius, T. J. Prakt. Chem. 1914, 87, 513
Heiduschka, A.; Langkammerer, H. J. Prakt. Chem. 1914, 88, 425
Hiller, S. J. Prakt. Chem. 1914, 88, 731
Busch, M.; Lotz, H. J. Prakt. Chem. 1914, 90, 257
Brady, O.L.; Dunn, F.P. J. Chem. Soc. 1914, 105, 2409; 2872
Brady, O.L.; Dunn, F.P. Proc. Chem. Soc. 1914, 30, 240; 292
Raffo, M.; Rossi, G. Gazz. Chim. Ital. 1915, 45, 28
von Meyer, F. J. Prakt. Chem. 1915, 92, 255
Chattaway, F.D.; Clemo, G.R. J. Chem. Soc. 1916, 109, 89
Poccianti, P. Atti Accad. Lincei 1915, 24, 1135
Poccianti, P. Gazz. Chim. Ital. 1915, 45, 111
Brady, O.L.; Dunn, F.P. J. Chem. Soc. 1916, 109, 650
Andreasch, R. Monatsch. Chem. 1917, 38, 203
organolithium compounds
Schlenk, W.; Holtz, J. Chem. Ber. 1917, 50, 271
Andreasch, R. J. Chem. Soc. 1918, 114, 80
Conant, J.B.; Wheland, G.W. J. Am. Chem. Soc. 1932, 54, 1212 (stabilities of carbanions from hydrocarbon acidities)
Carbanions via E1cb (elimination unimolecular carbanion) mechanism

28
+
NMe3
Ar

_

_

+
NMe3

+ H2O

Ar

+ H 3 O+

+
NMe3

Ar

Ar

+ NMe3

Ar = p-NO2 -C6 H4
Hughes, E.D.; Ingold, C.K. J. Chem. Soc. 1933, 523
Hughes, E.D.; Ingold, C.K.; Patel, C.S. J. Chem. Soc. 1933, 526
Carbenes or methylenes (general)
Reviews:
Huisgen, R. Angew. Chem. 1955, 67, 439
Knunyants, I.L.; Gambaryan, N.P.; Rokhin, E.M. Usp. Khim. 1958, 27, 1361
Kirmse, W. Angew. Chem. 1959, 71, 537
Kirmse, W. Angew. Chem. 1961, 73, 161
Zollinger, H. Azo and Diazo Chemistry: aliphatic and aromatic compounds, Interscience Publications, Inc.: New York, 1961
Miginiac, P. Bull. Soc. Chim. Fr. 1962, 2000
Chinoporos, E. Chem. Rev. 1963, 63, 235
Parham, W.E.; Schweizer, E.E. Org. Reactions 1963, 13, 55
Hine, J. Divalent Carbon, Ronald Press: New York, 1964
Kirmse, W. Carbene Chemistry, Academic Press: New York, 1964
DeMore, W.B.; Benson, S.W. Adv. Photochem. 1964, 2, 219
Frey, H.M. Prog. Reaction Kinetics 1964, 2, 131
Bell, J.A. Prog. Phys. Org. Chem. 1964, 2, 1
Closs, G.L. Top. Stereochem. 1968, 3, 193
Gilcrist, T.L.; Rees, C.W. Carbenes, Nitrenes, and Arynes, Appleton-Century-Crofts: New York, 1969
Bethell, D. Adv. Phys. Org. Chem. 1969, 7, 153
Jones, M. Jr.; Moss, R.A. Carbenes, Wiley-Interscience: New York, Vol. 1 - 2, 1973
Bethell, D. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 61
Bethell, D. Org. Reactive Intermed. 1973, 61

29
Connor, J.A. J. Organometallic Chem. 1975, 4, 235 (carbenes and carbynes)
Moss, R.A.; Jones, M. (eds.) Carbenes, Vol. 1, 2, Wiley: New York, 1975
Moss, R.A. Acc. Chem. Res. 1980, 13, 58
Griller, D.; Nazran, A.S.; Scaiano, J.C. Acc. Chem. Res. 1984, 17, 283
Platz, M.S. (ed.) Kinetics and Spectroscopy of Carbenes and Biradicals, Plenum Press: New York, 1990
Tomioka, H. Res. Chem. Intermediates 1994, 20, 605
Liu, M.T.H. Acc. Chem. Res. 1994, 27, 287
Regitz, M. Angew. Chem. Int. Ed. 1996, 35, 725
Zaragoza, F. Tetrahedron 1997, 53, 3425
Tomioka, H. Acc. Chem. Res. 1997, 30, 315
Tomioka, H. Bull. Chem. Soc. Jpn 1998, 71, 1501
Arnold, B.R.; Bucher, G.; Netto-Ferreira, J.C.; Platz, M.S.; Scaiano, J.C. Biradicals, Radicals in Excited States, Carbenes, and Related Species,
Springer-Verlag: Weinheim, 1998
Böhm, V.P.W.; Herrmann, W.A. Angew. Chem. Int. Ed. 2000, 39, 4036 (stable carbenes)
Bertrand, G. (ed.) Carbene Chemistry: from fleeting intermediates to powerful reagents, Marcel Dekker, Inc.: New York, 2002
P2 O5

: CH2

CH3 OH

Dumas, J.B.; Peligot, E. Ann. Chim. Phys. 1835, 58, 5 (attempt)
Regnault, H.V. Ann. Chim. Phys. 1839, 71, 427
base
CHCl3

: CCl2

- HCl

Geuther, A. Ann. Chem. 1862, 123, 121 (suggestion)

CH2 I2



:

: CH2

CH2
CH2 =CH 2
Cu
Butlerov, A. Ann. Chem. 1858, 107, 110
Butlerov, A. Ann. Chem. 1859, 111, 242
Nef, J.U. Ann. Chem. 1897, 298, 202 (general methylene theory)

30
O
N2

R1

- N2

R2

hν or ∆

:

hν or ∆
R1

R2

C

- CO
R1

R2

Staudinger, H.; Kupfer, O. Chem. Ber. 1911, 44, 2197
Staudinger, H.; Kupfer, O. Chem. Ber. 1912, 45, 501 (from diazomethanes and diazoketones)
Meerwein, H.; Rathjen, H.; Werner, H. Chem. Ber. 1942, 75, 1610 (discovery of insertion reactions of carbenes in XH bonds)
Doering, W.v.E.; Knox, L.H. J. Am. Chem. Soc. 1956, 78, 4947 (coining of name)
CHCl3 + OH-

H2 O + CCl3 -

:CCl2

CCl3 -

+ Cl-

Hine, J. J. Am. Chem. Soc. 1950, 72, 2438 (haloform hydrolysis)
Hine, J.; Dowell, A.M. Jr. J. Am. Chem. Soc. 1954, 76, 2688
Hine, J.; Dowell, A.M. Jr.; Singley, J.E. Jr. J. Am. Chem. Soc. 1956, 78, 479

:

.
.

R

R

R

R
Y

Y

X

X
R

R

R
Y

X

R

R

R

Y

X

X

Y

31
Doering, W.v.E.; Hoffmann, A.K. J. Am. Chem. Soc. 1954, 76, 6162 (trapping of carbenes with olefins)
Skell, P.S.; Garner, A.Y. J. Am. Chem. Soc. 1956, 78, 3409 (connection between multiplicity of carbene and stereochemistry of cyclopropane trapped
product)
Skell, P.S.; Garner, A.Y. J. Am. Chem. Soc. 1956, 78, 5430 (connection between multiplicity of carbene and stereochemistry of cyclopropane trapped
product)
O

O
H

N2

COOR

H

- N2 RO

:

RO

COOR

ROOC

COOR

Doering, W.v.E.; Knox, L.H. J. Am. Chem. Soc. 1956, 78, 4947 (coining of "carbene" name)
Doering, W.v.E.; Henderson, W.A. Jr. J. Am. Chem. Soc. 1958, 80, 5274
R-H
T = 77 K

Ph

Ph

+ Ph 2 C=CPh 2

:

N2

254 nm
Ph

Ph

- N2

Ph

Ph
H

R-H
T > 77 K

Ph

.
Ph

+ R

.

32

Gibbons, W.A.; Trozzolo, A.M. J. Am. Chem. Soc. 1966, 88, 172 (matrix isolation EPR)

:

N2
H



R-H

- N2

-R

.

.

Moritani, I.; Murahashi, S.; Nishino, N.B.; Kimura, K.; Tsubomura, H. Tetrahedron Lett. 1966, 373 (flash photolysis of diazo compounds - no
kinetics)


N2

benzene
Ph

Ph

Ph
H


cyclohexane

Ph

..
.

Ph

Ph

λ(max) = 300 nm

λ(max) = 340 nm

Closs, G.L.; Rabinow, B.E. J. Am. Chem. Soc. 1976, 98, 8190 (first absolute rate constant measurement of carbene reaction by flash photolysis)

:

Moss, R.A.; Mallon, C.B. J. Am. Chem. Soc. 1975, 97, 344 (Hammett analysis of carbene + olefin reaction)
Moss, R.A.; Joyce, M.A.; Huselton, J.K. Tetrahedron Lett. 1975, 16, 4621

Ar

Cl

Turro, N.J.; Butcher, J.A. Jr.; Moss, R.A.; Guo, W.; Munjal, R.C.; Fedorynski, M. J. Am. Chem. Soc. 1980, 102, 7576
Gould, I.R.; Turro, N.J.; Butcher, J. Jr.; Doubleday, C. Jr.; Hacker, N.P.; Lehr, G.F.; Moss, R.A.; Cox, D.P.; Guo, W.; Munjal, R.C.; Perez, L.A.;
Fedorynski, M. Tetrahedron 1985, 41, 1587

:

33

Zupanic, J.J.; Schuster, G.B. J. Am. Chem. Soc. 1980, 102, 5958
Lapin, S.C.; Brauer, B.E.; Schuster, G.B. J. Am. Chem. Soc. 1984, 106, 2092

Ph

.
.

Ph

Hadel, L.M.; Platz, M.S.; Scaiano, J.C. J. Am. Chem. Soc. 1984, 106, 283 (quenching of triplet diphenylcarbene)
Griller, D.; Nazran, A.S.; Scaiano, J.C. Tetrahedron 1985, 41, 1525

(CH3) 2C=O

Np

_

O+

H

CH3CN


Np

H - N2

Np

_

:

N2
Np

N+

H
Np

H
N

_

N+

H

Et3N

Np

_
H

+
NEt 3

34

Barcus, R.L.; Hadel, L.M.; Johnston, L.J.; Platz, M.S.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1986, 108, 3928
(trapping of carbenes via ylide formation)
X+

_

Griller, D.; Hadel, L.M.; Nazran, A.S.; Platz, M.S.; Wong, P.C.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1984, 106, 2227
(trapping of carbenes via ylide formation)
O

O

R

R

R


- N2
R

R

R

R

..

.

O
R

R

R = H, F
R

R

.

R

N2

Sander, W.; Bucher, G.; Reichel, F.; Cremer, D. J. Am. Chem. Soc. 1991, 113, 5311
Bucher, G.; Sander, W. J. Org. Chem. 1992, 57, 1346
Wenk, H.H.; Hübert, R.; Sander, W. J. Org. Chem. 2001, 66, 7994
Sander, W.; Hübert, R.; Kraka, E.; Grafenstein, J.; Cremer, D. Chem. Eur. J. 2000, 6, 4567

..

Carbenes (singlet)

R1

Reviews:

R2

35
Kirmse, W. Angew. Chem. Int. Ed. 2004, 43, 1767
Herzberg, G.; Shoosmith, J. Nature 1959, 183, 1801
Herzberg, G. Proc. Roy. Soc. London 1961, 262A, 291
Mackay, C.; Wolfgang, R. J. Am. Chem. Soc. 1961, 83, 2399
Gutsche, C.D.; Bachman, G.L.; Coffey, R.S. Tetrahedron 1962, 18, 617
Bradley, J.N.; Ledwith, A. J. Chem. Soc. 1963, 3480
Schoellkopf, U.; Lerch, A.; Paust, J. Chem. Ber. 1963, 96, 2266
Skatteboel, L. Acta Chem. Scand. 1963, 17, 1683
Bradley, J.N.; Cowell, G.W.; Ledwith, A. J. Chem. Soc. 1964, 353
Hamilton, G. J. Am. Chem. Soc. 1964, 86, 3391
Sargeant, P.B.; Shechter, H. Tetrahedron Lett. 1964, 3957
Herzberg, G.; Johns, J.W.C. Proc. Roy. Soc. London 1967, 295A, 107

..

Carbenes (triplet)

R1

R2

Reviews:
Tomioka, H. Acc. Chem. Res. 1997, 30, 315
Kirmse, W. Angew. Chem. Int. Ed. 2003, 42, 2117
Herzberg, G.; Shoosmith, J. Nature 1959, 183, 1801
Herzberg, G. Proc. Roy. Soc. London 1961, 262A, 291
Skell, P.S.; Klebe, J. J. Am. Chem. Soc. 1960, 82, 247
MacKay, C.; Wolfgang, R. J. Am. Chem. Soc. 1961, 83, 2399
Schoellkopf, U.; Lerch, A.; Pitteroff, W. Tetrahedron Lett. 1962, 241
D'yakonov, I.A.; Danilkina, L.P. Zh. Obshch. Khim. 1962, 32, 1008
Bradley, J.N.; Ledwith, A. J. Chem. Soc. 1963, 3480

36
Cowan, D.O.; Couch, M.M.; Kopecky, K.R.; Hammond, G. J. Org. Chem. 1964, 29, 1922
Sloan, M.F.; Prosser, T.J.; Newburg, N.R.; Breslow, D.S. Tetrahedron Lett. 1964, 2945
Hamilton, G.A. . J. Am. Chem. Soc. 1964, 86, 3391
Frey, H.M. Chem. Commun. 1965, 260
Padwa, A.; Layton, R. Tetrahedron Lett. 1965, 2167
Moritani, I.; Obata, N. Tetrahedron Lett. 1965, 2817
Carbene (Arduengo)
Reviews:
Arduengo, A.J. III Acc. Chem. Res. 1999, 32, 913 (stable carbenes)
Arduengo, A.J. III Tetrahedron 1999, 55, 14523 (imidazolylidenes and imidazolinylidenes)

+
N

N

:

KOtBu
THF
N

- KCl
- tBuOH

Cl-

N

Arduengo, A.J. III; Harlow, R.L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361
Dixon, D.A.; Arduengo, A.J. III J. Phys. Chem. 1991, 95, 4180
Arduengo, A.J. III; Dias, H.V.R.; Harlow, R.L.; Kline, M. J. Am. Chem. Soc. 1992, 114, 5530
Carbene (Bertrand)
Reviews:
Bertrand, G. Chem. Rev. 2000, 100, 39 (stable carbenes)
N2

Me3Si

Li

+ (iPr2 N)2 PCl

N2

THF
- 78o C
- LiCl

N(iPr)2
Me3Si

P
N(iPr)2

37
N2

:

_

N(iPr)2
Me3Si



P

N(iPr)2
Me3Si

- N2

+

P

Me3Si

N(iPr)2

N(iPr)2

N(iPr)2

P

N(iPr)2
Me3Si

C

N(iPr)2

N(iPr)2

Baceiredo, A.; Bertrand, G.; Sicard, G. J. Am. Chem. Soc. 1985, 107, 4781
Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 6463
Igau, A.; Baceiredo, A.; Trinquier, G.; Bertrand, G. Angew. Chem. Int. Ed. 1989, 28, 621
Dicarbenes
N2

:

:

N2



.

- 2 N2

Trozzolo, A.M.; Murray, R.W.; Smolinsky, G.; Yager, W.A.; Wasserman, E. J. Am. Chem. Soc. 1963, 85, 2526

Ph

Ph



Ph

:

N2

:

N2

Ph

- 2 N2
Wasserman, E.; Murray, R.W.; Yager, W.A.; Trozzolo, A.M.; Smolinksy, G. J. Am. Chem. Soc. 1967, 89, 5076
Carbocations

P

.

38
R1

R3

+

R2

Reviews:
Ingold, C.K. Ann. Rep. Prog. Chem. (Chem. Soc. London) 1927, 24, 156
Whitmore, F.C. Ann. Rep. Prog. Chem. (Chem. Soc. London) 1933, 30, 177
Whitmore, F.C. Chem. Eng. News 1948, 26, 688
Deno, N.C. Prog. Phys. Org. Chem. 1964, 2, 129
Olah, G.; Pittman, C.U. Jr. Adv. Phys. Org. Chem. 1966, 4, 305
Bethell, D.; Gold, V. Carbonium Ions: an introduction, Academic Press: London, 1967
More O'Ferrall, R.A. Adv. Phys. Org. Chem. 1967, 5, 331
Olah, G.A.; Schleyer, P.v.R., eds. Carbonium Ions, Wiley-Interscience: New York, 1968 - 1976, Vol. I - IV, 1968 - 1973
Nenitzescu, C.N. in Carbonium Ions (G.A. Olah; P.v.R. Schleyer, eds.) Wiley-Interscience: New York, 1968, Vol. 1, p. 1 - 75
Cacace, F. Adv. Phys. Org. Chem. 1970, 8, 79
Brouwer, D.M.; Hogeveen, H. Prog. Phys. Org. Chem. 1972, 9, 179
Hogeveen, H. Adv. Phys. Org. Chem. 1972, 10, 29
Cabell-Whiting, P.W.; Hogeveen, H. Adv. Phys. Org. Chem. 1972, 10, 129
McManus, S.P.; Pittman, C.U. Jr. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 193
Olah, G.A. Carbocations and Electrophilic Reactions, Wiley: New York, 1974
Ahlberg, P.; Jönsall, G.; Engdahl, C. Adv. Phys. Org. Chem. 1983, 19, 223
Olah, G.A.; Prakash, G.K.S.; Sommer, J. Superacids, Wiley: New York, 1985
Vogel, P. Carbocation Chemistry, Elsevier: Amsterdam, 1985
Traynham, J.G. J. Chem. Educ. 1986, 63, 930 (carbocation names)
Traynham, J.G. J. Chem. Educ. 1989, 66, 451 (carbocation names)
Prakash, G.K.S.; Schleyer, P.v.R. Stable Carbocation Chemistry, Wiley: New York, 1997
Rappoport, Z.; Stang, P.J. Diccoordinated Carbocations, Wiley: New York, 1997
Abboud, J.L.M.; Herreros, M.; Notario, R.; Lomas, J.S.; Mareda, J.; Müller, P.; Rossier, J.C. J. Org. Chem. 1999, 64, 6401 (bridgehead
carbocations)
Richard, J.P.; Amyes, T.L.; Lin, S.S.; O'Donoghue, A.C.; Toteva, M.M.; Tsuji, Y.; Williams, K.B. Adv. Phys. Org. Chem. 2000, 35, 67
Olah, G.A. J. Org. Chem. 2001, 65, 5943
Abboud, J.L.M.; Alkorta, I.; Dávalos, J.Z.; Müller, P.; Quintanilla, E. Adv. Phys. Org. Chem. 2002, 37, 57
stabilities of carbocations:

39
Deno, N.C.; Jaruzelski, J.; Schriescheim, A. J. Am. Chem. Soc. 1955, 77, 3044 (triarylcarbonium ions by HR acidity function)
Jenson, E.D.; Taft, R.W. J. Am. Chem. Soc. 1964, 86, 116 (triarylcarbonium ions by potentiometric measurements)
Taft, R.W.; McKeever, L.D. J. Am. Chem. Soc. 1965, 87, 2489 (triarylcarbonium ions by potentiometric measurements)
Diffenbach, R.A.; Sano, K.; Taft, R.W. J. Am. Chem. Soc. 1966, 88, 4747 (triarylcarbonium ions by potentiometric measurements)
Feldman, M.; Flythe, W.C. J. Am. Chem. Soc. 1969, 91, 4577 (triarylcarbonium ion reduction potentials)
Breslow, R.; Balasubramanian, K. J. Am. Chem. Soc. 1969, 91, 5182 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Chu, W. J. Am. Chem. Soc. 1970, 92, 2165 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Chu, W. J. Am. Chem. Soc. 1973, 95, 411 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Mazur, M. J. Am. Chem. Soc. 1973, 95, 584 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Drury, R.F. J. Am. Chem. Soc. 1974, 96, 4702 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R. Pure Appl. Chem. 1974, 40, 493 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Wasielewski, M.R.; Breslow, R. J. Am. Chem. Soc. 1976, 98, 4222 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Breslow, R.; Goodin, R. J. Am. Chem. Soc. 1976, 98, 6077 (thermodynamic stabilities of cations and anions via electrochemical oxidations)
Bank, S.; Ehrlich, C.L.; Zubieta, J.A. J. Org. Chem. 1979, 44, 1454 (trityl carbonium ions)
Bank, S.; Ehrlich, C.L.; Mazur, M.; Zubieta, J.A. J. Org. Chem. 1981, 46, 1243 (trityl carbonium ions)
Cl

H2 O
acid catalyst

OH

Stieglitz, J. Am. Chem. J. 1899, 21, 101
Ph

H2 SO4

Ph
Cl

+ AlCl3
Ph

Ph

+
Ph

AlCl4 Ph

Norris, J.F.; Sanders, W.W. Am. Chem. J. 1901, 25, 54
Norris, J.F. Am. Chem. J. 1901, 25, 117
Norris, J.F. Am. Chem. J. 1907, 38, 627

MeO

C

MeO

Cl

C+

- HCl
3

3

HSO4 -

40

Ph
Cl

Ph

H2 SO4

Ph

HSO4 Ph

Ph

HCl

+

Ph

SO4 -2

Ph

Ph

+

Ph

2
Gomberg, M. Chem. Ber. 1902, 35, 2397; 2405
Walden, P. Chem. Ber. 1902, 35, 2018
Hantzsch, A. Z. Physik. Chem. 1907, 61, 257
Hantzsch, A. Chem. Ber. 1921, 54, 2573; 2578
H2 N

H2 N

+

+

NH2

X

H2 N

-

NH2

X-

H2 N

fuchsine

41
Me2N

Me2N

+

+

NMe2

X

-

NMe2

X

crystal violet

-

Me2N

Me2N

Kehrmann, F.; Wentzel, F. Chem. Ber. 1901, 34, 3815
Baeyer, A.; Villiger, V. Chem. Ber. 1902, 35, 1189
Baeyer, A.; Villiger, V. Chem. Ber. 1902, 35, 3013
Baeyer, A.; Villiger, V. Chem. Ber. 1903, 36, 2774
Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 597
Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 1183
Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 2848
Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 3191
Baeyer, A. Chem. Ber. 1905, 38, 569
Baeyer, A. Chem. Ber. 1905, 38, 1156

Cl

- Cl-

Ph
Cl

Ph

H2 O
80% EtOH

OR

- Cl-

Ph

R = H, Et

OR

H2 O
80% EtOH
Ph

+

Ph

+
Ph

Ph

Ph

Ph

42
Ward, A.M. J. Chem. Soc. 1927, 445; 2285

Ph

Cl

+
Ph-CH 2

- Cl-

NaOH
Ph

- Na+

OH

Ingold, C.K.; Rothstein, E. J. Chem. Soc. 1928, 1217
Steigman, J.; Hammett, L.P. J. Am. Chem. Soc. 1937, 59, 2536
Whitmore, F.C. J. Am. Chem. Soc. 1932, 54, 3274

+

H+

Cl

- Cl-

+

Cl-

ClCl

Wagner, G.; Brickner, W. Chem. Ber. 1899, 32, 2302
Meerwein, H.; van Emster, K. Chem. Ber. 1922, 55, 2500
Meerwein, H.; Hammel, O.; Serini, A.; Vorster, J. Ann. Chem. 1927, 453, 16
Ziegler, K.; Wollschitt, H. Ann. Chem. 1930, 479, 104 (stabilities of cations in SO2)
R-F + BF 3

R+ BF4 -

R = tBu, iPr

Olah, G.A.; Kuhn, S.J.; Opal, J. J. Chem. Soc. 1957, 2174

Cl

43
O

O

+ SbF 6 -

+ SbF 5
tBu

F

tBu

- CO

Me3 C+ SbF 6 -

Olah, G.A.; Kuhn, S.J.; Tolgyesi, W.S.; Baker, E.B. J. Am. Chem. Soc. 1962, 84, 2733
Olah, G.A. Rev. Roum. Chim. 1962, 7, 1129
R

FSO3 H-SbF 5
R

H

R3 C+ FSO3 - + H 2

R

Olah, G.A.; Lukas, J. J. Am. Chem. Soc. 1967, 89, 2227; 4743
Olah, G.A.; Tolgyesi, W.S.; Kuhn, S.J.; Moffatt, M.E.; Bastien, I.J.; Baker, E.B. J. Am. Chem. Soc. 1963, 85, 1328
Olah, G.A.; Comisarow, M.B.; Cupas, C.A.; Pittman, C.U. Jr. J. Am. Chem. Soc. 1965, 87, 2997
Olah, G.A.; Schlosberg, R.H. J. Am. Chem. Soc. 1968, 90, 2726
Olah, G.A. J. Am. Chem. Soc. 1972, 94, 808 (proposal to change definition of carbonium ion; introduction of carbenium ion terminology)

.

Carbynes
C

:

R

Reviews:
Connor, J.A. J. Organometallic Chem. 1975, 4, 235 (carbenes and carbynes)
N2

_

+2

Hg + 2 N 2 + 2 EtOOC

.
C

:

Hg



EtOOC

2

44

Strausz, O.P.; Kennepohl, G.J.A.; Garneau, F.X.; DoMinh, T.; Kim, B.; Valenty, S.; Skell, P.S. J. Am. Chem. Soc. 1974, 96, 5723
2,4- and 2,5-Cyclohexadienones
O
O

R
R

H

H

Reviews:
Schuster, D.I. Acc. Chem. Res. 1978, 11, 65
Crowther, H.L.; McCombie, H. J. Chem. Soc. 1913, 103, 536
Crowther, H.L.; McCombie, H. Proc. Chem. Soc. 1913, 29, 68
O - Na+

O

Br

+

- NaBr
Curtin, D.Y.; Crawford, R.J. Chem. Ind. 1956, 313
2,4- and 2,5-Cyclohexadienimines
R1
N
R2

N
R1

H

R2

H

45

Reviews:
None
Cl
NH2
F

N
F

2 tBuOCl

F

F

F

F

- 2 tBuOH
F

F

R

R

Cl

R = Me, MeO, nBu
Andreevskaya, O.I.; Markovskii, L.N.; Poleshchuk, O.K.; Furin, G.G.; Shermolovich, Y.G.; Yakobson, G.G. Zh. Org. Khim. 1980, 16, 817

COOH
H2 N

O

pTolSO2 Cl pTolSO2

O
N

O

H2 O /
alumina
O
- pTolSO2 NH 2

O

- HCl
- 2 H+
- 2 eCoutts, I.G.C.; Edwards, M.; Musto, D.R.; Richards, D.J. Tetrahedron Lett. 1980, 21, 5055

R2
tBu

R1

R2

tBu

H

+
N+
tBu

O-

R1

H

+

O

tBu

R3
R1

N

R3
tBu

N

R2

O
R3

tBu

46
Doepp, D.; Krueger, C.; Makedakis, G.; Nour-el-Din, A.M. Chem. Ber. 1985, 118, 510
Cyclopropenyl cations
R1

R1

R1

R1

+
+

+
+

R2

R2

R3

R3

R2

R3

R2

Reviews:
Krivun, S.V.; Alferova, O.F.; Sayapina, S.V. Usp. Khim. 1974, 43, 1739
Allen, A.D.; Tidwell, T.T. Chem. Rev. 2001, 101, 1333
Komatsu, K.; Kitagawa, T. Chem. Rev. 2003, 103, 1371
Ph

Ph

N2

Cl

OtBu

tBuOH

+
Ph

Ph

Cl

- HCl

- N2
Ph

Ph

Ph

Ph

Ph
Ph

Ph

H2 O

Ph

Ph

O

HBF 4
+

Ph

Ph

Ph

Breslow, R. J. Am. Chem. Soc. 1957, 79, 5318

Ph

BF4 Ph

R3

47
Breslow, R.; Yuan, C. J. Am. Chem. Soc. 1958, 80, 5991
Breslow, R.; Höver, H. J. Am. Chem. Soc. 1960, 82, 2644
Breslow, R.; Bahary, W.; Reinmuth, W. J. Am. Chem. Soc. 1961, 83, 1763
Breslow, R.; Lockhart, J.; Chang, H.W. J. Am. Chem. Soc. 1961, 83, 2375
Breslow, R.; Höver, H.; Chang, H.W. J. Am. Chem. Soc. 1962, 84, 3168
Breslow, R.; Groves, J.T.; Ryan, G. J. Am. Chem. Soc. 1967, 89, 5048
Dications
Reviews:
Nenajdenko, V.G.; Shevchenko, N.E.; Balenkova, E.S.; Alabugin, I.V. Chem. Rev. 2003, 103, 229
(i) Benzidine rearrangement
2 H+

+

NH NH

H

+

+

H2 N

+

NH2 NH2

- 2 H+
H2 N

NH2

NH2

H

Hofmann, A.W. Proc. Roy. Soc. London 1863, 12, 576
Jacobson, P.; Henrich, F.; Klein, J. Chem. Ber. 1893, 26, 688
Olah, G.A.; Dunne, K.; Kelly, D.P.; Mo, Y.K. J. Am. Chem. Soc. 1972, 94, 7438
(ii) Dications synthesized in magic acid
O

O

FSO3 H/
SbF 5 /SO2

O

+O

(CH2)n

(CH2)n
HO

O

OH

H2 O

+

- 2 H2 O
OH2

+

C

(CH2)n

C

O+

[SbF 6 -]2

48
Olah, G.A.; Comisarow, M.B. J. Am. Chem. Soc. 1966, 88, 3313
FSO3 H/
R1
R1
SbF 5 /SO2
+
OH

N

H

R1
H

OH2

N+

R2

+

N+

- H2 O

R2

[SbF 6 -]2

R2

Olah, G.A.; Calin, M. J. Am. Chem. Soc. 1968, 90, 943
R

R
R

FSO3 H/
X SbF 5 /SO2

R

X
R

R = H, Ph

[SbF 6 -]2

+2
- 2 HX

X = Cl, Br
R

R

R

Olah, G.A.; Bollinger, J.M.; White, A.M. J. Am. Chem. Soc. 1969, 91, 3667
Olah, G.A.; Mateescu, G.D. J. Am. Chem. Soc. 1970, 92, 1430

FSO3 H/
SbF 5 /SO2

[SbF 6 -]2

+

+

Bollinger, J.M.; Olah, G.A. J. Am. Chem. Soc. 1969, 91, 3380
(iii) Violenes
- eR2 N

CH

CH

CH

CH

NR2

n

.
+

R2 N

CH

CH

CH

CH

NR2

n

- e-

+
R2 N

+
CH

CH

CH

CH

NR2

n

49

Hunig, S. Ann. Chem. 1964, 676, 32
Hunig, S.; Balli, H.; Conrad, H.; Schott, A. Ann. Chem. 1964, 676, 36; 52
Hunig, S. Chem. Eng. News 1966, 44, 102
Hunig, S.; Geiger, H.; Kaupp, G.; Kniese, W. Ann. Chem. 1966, 697, 116
(iv) Wallach intermediate

Ar

N

+

+

N

N

Ph

2 H+

N+
O-

- H2 O

Ar

+

+

N

N

H2 O
-H

+
Ar

N

Cox, R.A.; Fung, D.Y.K.; Csizmadia, I.G.; Buncel, E. Can. J. Chem. 2003, 81, 535

+
H2 N

+
NH2

Ar

N

+

Wallach, O.; Belli, E. Chem. Ber. 1880, 13, 525
Buncel, E.; Lawton, B.T. Chem. Ind. 1963, 1835
Buncel, E.; Lawton, B.T. Can. J. Chem. 1965, 43, 862
Olah, G.A.; Dunne, K.; Kelly, D.P.; Mo, Y.K. J. Am. Chem. Soc. 1972, 94, 7438

(v) Wurster salts

OH

H

-H

+

N

N

OH

50

Me2N

NMe2

HOAc

.

+ Br-

.

+ Br-

+

Br2
Me2N

NMe2

Wurster's blue

Me2N

NH2

+

Br2
HOAc

Me2N

NH2

Wurster's red
Wurster, C. Chem. Ber. 1879, 12, 522
Wurster, C.; Sendtner, R. Chem. Ber. 1879, 12, 1803
Wurster, C.; Schobig, E. Chem. Ber. 1879, 12, 1807
Wurster, C. Chem. Ber. 1879, 12, 2071
Wurster, C. Chem. Ber. 1886, 19, 3195

.

+ NMe2

NMe2

- e-

NMe2

+ NMe2
- e-

NMe2

+ NMe2

Michaelis, L. J. Am. Chem. Soc. 1931, 53, 2953
Katz, H. Z. Physik 1933, 87, 238
Michaelis, L.; Schubert, M.P.; Granick, S. J. Am. Chem. Soc. 1939, 61, 1981
1,3-Dioxolenium salts

51
O

R
+

BF4 -

O

Reviews:
Paulsen, H. Pure Appl. Chem. 1975, 41, 69
O

O

+ AgBF4

Br

+

BF4 -

+ AgBr

O

O

Meerwein, H.; Wunderlich, K. Angew. Chem. 1957, 69, 481
Cl

Cl
O

Cl

N2

+

BF4

-

Ph

O

Ph

+

+

H
O

BF4 -

+

Cl

H

O

Cl

Cl

Meerwein, H.; Allendorfer, H.; Beckmann, P.; Kunert, F.; Morschel, H.; Pawellek, F.; Wunderlich, K. Angew. Chem. 1958, 70, 211
O

O

R

R

+ AgBF4 + Et-Br

+

O

BF4 -

+ AgBr + Et-H

O

Meerwein, H.; Hederich, V.; Wunderlich, K. Arch. Pharm. 1958, 291, 541
O

O
+

+ Ph 3 C BF4
O

H

-

+
O

BF4 -

+ Ph 3 CH

52

Meerwein, H.; Hederlich, V.; Morschel, H.; Wunderlich, K. Ann. Chem. 1960, 635, 1
1,3-Dipoles
carbene traps
+
+
R3

X

_
R2

R4

R1

_

R1

+

+

:

R1

X

R1

O
R5

R2
R4

R3

R2

C

N

_
R3

O-

carbonyl oxide

R2

nitrile ylides

carbonyl ylide (X = O)
thiocarbonyl ylide (X = S)
azomethine ylide (X = N-R)
Reviews:
Smith, L.I. Chem. Rev. 1938, 23, 193
Huisgen, R. Proc. Chem. Soc. 1961, 357
(i) Azomethine ylide
Reviews:
Surpateanu; Karzazi Heterocycles 1999, 51, 863 (cyclic azomethine ylides)
Eberbach, W. Science of Synthesis 2004, 27, 441
Huisgen, R. Angew. Chem. 1963, 75, 604
Huisgen, R. Angew. Chem. 1963, 75, 742
(ii) Carbonyl oxide (Criegee zwitterion)
Reviews:
Criegee, R. Record Chem. Prog. 1957, 18, 111
Bailey, R.S. Chem. Rev. 1958, 58, 925
Criegee, R. in Peroxide Reaction Mechanisms (J.O. Edwards, ed.) Interscience Publishers, Inc.: New York, 1962, p. 32

53
Huisgen, R. Angew. Chem. Int. Ed. 1963, 2, 565
Kuczkowski, R.L. in 1,3-Dipolar Cycloaddition Chemistry, (A. Padwa, ed.) Wiley: New York, 1984, Vol. 2, p. 197 - 276
Sander, W. Angew. Chem. 1990, 102, 362
Bunnelle, W.H. Chem. Rev. 1991, 91, 335
Ishiguro, K.; Nojima, T.; Sawaki, Y. J. Phys. Org. Chem. 1997, 10, 787
Block, K.; Kappert, W.; Kirschfeld, A.; Muthusamy, S.; Schroeder, K.; Sander, W.; Kraka, E.; Sosa, C.; Cremer, D. in Peroxide Chemistry, (W.
Adam, ed.) Wiley-VCH: Weinheim, 2000, p. 139 - 156
+ _
Ph2 C=N=N
Ph2 C

:


N2 + Ph 2 C
+ _
Ph2 C=O-O

+ O2

+ _
Ph2 C=O-O

+

:

+ _
Ph2 C=N=N

R

2 Ph2 C=O + N2

R
O+

+

O-

R

R

MeOH
O

O-

MeO

R

R

dimerization
R

O

R

O

O

O

OOH

R

CH2 =O

O

R
R
O

R

Bartlett, P.D.; Traylor, T.G. J. Am. Chem. Soc. 1962, 84, 3408

O

54
_
+
Ph2 C-O-O


Ph2 CN2

O

Ph

RCHO

- N2

R

Ph

H
O

O

Murray, R.W.; Suzui, A. J. Am. Chem. Soc. 1971, 93, 4963
R

1

+

_

N

R

O2

N

+

R

N

N
R

R

O

O-

R'-CHO

R

R'

O

O+
R

R

O

O

H

- N2

R

N
N

R

- N2

O-

O

N2 O + R2 C=O

O

Higley, D.P.; Murray, R.W. J. Am. Chem. Soc. 1974, 96, 3330
(iii) Carbonyl ylide
Reviews:
Padwa, A. Acc. Chem. Res. 1991, 24, 22
Padwa, A. Trends Org. Chem. 1993, 4, 139
McMills, M.C.; Wright, D. Chem. Heterocyclic Compounds 2002, 59, 253
Tomioka, H. in Nitrogen, Oxygen and Sulfur Ylide Chemistry, (J.S. Clark, ed.) Oxford University Press: Oxford, 2002, p. 213 - 218
Ph



_
Ph

Ph

∆ or hν

mCPBA

+
Ph

Ph

O

Ph

Ph

O+

Ph

55

Arnold, D.R.; Karnischky, L.A. J. Am. Chem. Soc. 1970, 92, 1404
O

Ph



Ph

O+

_

Ph

Ph

O+

O



Ph

O+

+

_

Ph
Ph

_

Ph
Ph

Ph

Thap, D.M.; Trozzolo, A.M.; Griffin, G.W. J. Am. Chem. Soc. 1970, 92, 1402
O

CN

Ph

O+

O

CN

COOEt
Ph

_
Ph

CN
CN

O+

CN

_
Ph

Robert, A.; Pommeret, J.J.; Foucaud, A. Compt. Rend. 1970, 270, 1739
Pommeret, J.J.; Robert, A. Compt. Rend. 1971, 272, 333
Pommeret, J.J.; Robert, A. Tetrahedron 1971, 27, 2977
Robert, A.; Pommeret, J.J.; Foucaud, A. Tetrahedron 1972, 28, 2085

CN
COOEt

56
O

O

O

Ph
Ph

Ph

RCH=CHR
R

_

O

O+

O
Ph

Ph

Ph

R

Lown, J.W.; Matsumoto, K. Can. J. Chem. 1971, 49, 3443
Vukov, V.; Crawford, R.J. Can. J. Chem. 1975, 53, 1367 (secondary deuterium kinetic isotope effects)
NC

O

CN

Ph

Ph

O+

PhC

_

O

NC

CPh

CN

Ph
Ph

Ph

CN

Ph

CN
Ph

Ph

Hamsberger, H.; Huisgen, R. Chem. Commun. 1971, 1190
O

O

O

N2

:

Cu
O

OMe

- N2

O

_
MeOOC-C

COOMe

O+

O

OMe

C-COOMe

OMe

O
MeO
COOMe

Ueda, K.; Ibata, T.; Takebayashi, M. Bull. Chem. Soc. Jpn 1972, 45, 2779

57

N2

Ph

Ph

- N2

O

:


tBuOH matrix/
- 196 C
Ph

Ph

Ph

Ph

Ph

O+

_

Ph

Ph

Ph

Ph

O

Ph

Ph
Ph

Tomioka, H.; Miwa, T.; Suzuki, S.; Izawa, Y. Bull. Chem. Soc. Jpn 1980, 53, 753
(iv) Nitrile ylide
Reviews:
Huisgen, R.; Grashey, R.; Sauer, J. in The Chemistry of Alkenes, (S. Patai, ed.) Wiley-Interscience: New York, 1964, p. 806
Padwa, A.; Carlsen, P.H.J. Reactive Intermediates 1982, 2, 55
Hansen, H.J.; Hiemgartner, H. in 1,3-Dipolar Cycloaddition Chemistry, (A. Padwa, ed.) Wiley: New York, 1984, p. 177
Wentrup, C.; Reisinger, A.; Qiao, G.G.; Visser, P. Pure Appl. Chem. 1997, 69, 847
NEt3

N

+

Ph

Cl

NO2

-

Ph

N+

NO2

CN

H

_
Ph

- Et3 NH Cl

N

CN
NO2

Huisgen, R.; Stangl, H.; Sturm, H.J.; Wagenhofer, H. Angew. Chem. 1962, 74, 31
Huisgen, R.; Stangl, H.; Sturm, H.J.; Wagenhofer, H. Angew. Chem. Int. Ed. 1962, 1, 50
Huisgen, R. Angew. Chem. Int. Ed. 1963, 2, 565; 633
Huisgen, R.; Raab, R. Tetrahedron Lett. 1966, 649
Huisgen, R. Helv. Chim. Acta 1967, 50, 2421
Huisgen, R. J. Org. Chem. 1968, 33, 2291
Huisgen, R. J. Org. Chem. 1976, 41, 403

58
Turro, N.J.; Cha, Y.; Gould, I.R.; Padwa, A.; Gasdaska, J.R.; Thomas, M. J. Org. Chem. 1985, 50, 4415

CH2 N2

- N2

: CH2

CH3 CN
CH3

+

_

N

CH2

N
A

N

B
A

B

B

Padwa, A.; Gasdaska, J.R.; Thomas, M.; Turro, N.J.; Cha, Y.; Gould, I.R. J. Am. Chem. Soc. 1986, 108, 6739
Turro, N.J.; Cha, Y.; Gould, I.R. J. Am. Chem. Soc. 1987, 109, 2101
R1
Cl

R1

R2
N

+
Ar

N

_



Ar

R1

- HCl
R2

Ar

N

R2

Ar = p-NO2 -C6 H4 ; R1 = {H, CF3 }; R2 = {H, CF3 }
Hegarty, A.F.; Eustace, S.J.; Tynan, N.M.; Pham-Tran, N.N.; Nguyen, M.T. J. Chem. Soc. Perkin Trans. 2 2001, 1239
Fergus, S.; Eustace, S.J.; Hegarty, A.F. J. Org. Chem. 2004, 69, 4663
(v) Thiocarbonyl ylide
Reviews:
Mloston, G.; Heingartner, H. Pol. J. Chem. 2000, 74, 1503 (thiocarbonyl ylides)
Mloston, G.; Heingartner, H. Chem. Heterocyclic Compounds 2002, 59, 315 (thiocarbonyl ylides)

A

59
O

R

_

S

S+

+

R
O

O
R

R

O

O

O

Wittig, G.; Knaus, E.; Niethammer, K. Ann. Chem. 1960, 630, 10
Mayer, R.; Kleinert, H.; Richter, S.; Gewald, K. Angew. Chem. 1962, 74, 118
Pedersen, C.T. Acta Chem. Scand. 1966, 20, 2314
R1
N
R1

N

S

S

_
R2

- N2 R1

R2

R2

S+
R3 C

R3

R4

CR4
R1

S

Kellogg, R.M.; Wassenaar, S. Tetrahedron Lett. 1970, 1987
Buter, J.; Wassenaar, S.; Kellogg, R.M. J. Org. Chem. 1972, 37, 4045
Ueno, Y.; Okawara, M. Bull. Chem. Soc. Jpn 1972, 45, 1797
Kellogg, R.M. J. Org. Chem. 1973, 38, 844
Buter, J.; Raynolds, P.W.; Kellogg, R.M. Tetrahedron Lett. 1974, 2901

R2

60
tBu
S

tBu

Ph

:

tBu

+
Ph

tBu

S+

_

Ph

S

S+

Ph

_

Ph

Ph

McGimpsey, W.G.; Scaiano, J.C. Tetrahedron Lett. 1986, 27, 547
nitrene traps

R3

R1

C

_

N

N

_

nitrilimines

R2

R2

carbonyl imines (X = O)
thiocarbonyl imines (X = S)
azomethine imines (X = N-R)

:

:

N

R2

+
R1

N

azonium imines

N

: :

X

+

R3

: :

R1

: :

+

R2

N

_

+
R1

N

O

N

_
(i) Azomethines
Reviews:
Boyer, J.H. Mechanisms of Molecular Migrations 1969, 2, 267

nitrosoimines

61

Bach, F.L. Jr.; Karliner, J.; van Lear, G.E. Chem. Commun. 1969, 1110
Boyer, J.H.; Frints, P.J.A. J. Heterocyclic Chem. 1970, 7, 59; 71
Ph

Ph
O



O

_

Ph

Ph

N

N+
O

O

Barik, R.; Kumar, C.V.; Das, P.K.; George, M.V. J. Org. Chem. 1985, 50, 4309
N3

NC
NC

CN

+
NC

CN

_
CN



N+

- N2

CN
NC

Murata, S.; Abe, S.; Tomioka, H. J. Org. Chem. 1997, 62, 3055
(ii) Azonium imines
Reviews:
None.
(iii) Carbonyl imines
Reviews:
Kayam, R.; Shizuka, H.; Sekiguchi, S.; Matsui, K. Bull. Chem. Soc. Jpn 1975, 48, 3309
Tomioka, H. Bull. Chem. Soc. Jpn 1998, 71, 1501
(iv) Nitrilimines

62
Reviews:
Granier, M.; Baceiredo, A.; Gruetzmacher, H.; Pritzkow, H.; Bertand, G. Angew. Chem. Int. Ed. 1990, 102, 671
(v) Nitrosoimines
Reviews:
Akiba, K.; Inamoto, N. Heterocycles 1977, 7, 1131
Challis, B.C.; Challis, J.A. in The Chemistry of Amino, Nitroso, Nitro Compounds and Their Derivatives (S. Patai, ed.) Wiley: Chichester, 1982,
Vol. 2, p. 1151
(vi) Thiocarbonyl imines
Reviews:
None.
Doering-Zeiss intermediate
R2

H

R3

O
R

R
X

R1

H

O

63
HOOC
CH3

CH3

MeOH Me

O

O
HiPrCH
2

Et
O

H

OMe

Me

O

O
HiPrCH
2

O
Et

- ArCOO-

CH3

Me
O

Et H

Ar

- ArCOOH
- OMe-

- MeOH
- MeOH
CH3

CH3

Me

O+

O+
HiPrCH
2

Et

iPrCH 2

CH3

CH3
CH2 iPr

MeO

Et

Doering, W.v.E.; Zeiss, H.H. J. Am. Chem. Soc. 1953, 75, 4733
Enols and Enolates
OR3
R1

R3
R1

R2

R2

+ H+

Et H

- H+

- H+

OH

Me

iPrCH 2
Et

OMe

64
Reviews:
Toullec, J. Adv. Phys. Org. Chem. 1982, 18, 1
Rappoport, Z.; Biali, S.E. Acc. Chem. Res. 1988, 21, 442 (sterically crowded simple enols)
Rappoport, Z. (ed.) The Chemistry of Enols, Wiley: Chichester, 1990
Kresge, A.J. Acc. Chem. Res. 1990, 23, 43
Rochlin, E. Pure Appl. Chem. 1997, 69, 1933
Wirz, J. Pure Appl. Chem. 1998, 70, 2221
Erlenmeyer, E. Chem. Ber. 1875, 8, 309 (first suggestion)
Erlenmeyer, E. Chem. Ber. 1881, 14, 320
Wheeler, A.S.; Edwards, V.C. Ann. Chem. 1895, 286, 27
Knorr, L. Ann. Chem. 1899, 306, 363
Lapworth, A.; Hann, A.C.O. J. Chem. Soc. 1902, 1508
Lapworth, A. J. Chem. Soc. 1904, 30
Moore, T.S. J. Chem. Soc. 1907, 91-92, 1373
Dimroth, O. Chem. Ber. 1907, 40, 2404
Zelinsky, N.; Schlesinger, N. Chem. Ber. 1907, 40, 2886
Wohl, A.; Claussner, P. Chem. Ber. 1907, 40, 2308
Wohl, A. Chem. Ber. 1907, 40, 2282
Stoermer, R.; Martinsen, O. Ann. Chem. 1907, 352, 322
Petrenko-Kritshenko, P. J. Russ. Phys. Chem. Soc. 1907, 39, 179
Hantzsch, A. Chem. Ber. 1907, 40, 15; 23; 42
Stobbe, H. Ann. Chem. 1907, 352, 132
Henle, F. Ann. Chem. 1907, 352, 45
Piutti, A. Gazz. Chim. Ital. 1907, 36, 364
Bulow, C.; Busse, F. Chem. Ber. 1906, 39, 3861
Kohler, E.P. Am. Chem. J. 1907, 36, 529
Meyer, K.H. Ann. Chem. 1911, 380, 212;220
Meyer, K.H.; Kappelmeier, P. Chem. Ber. 1911, 44, 2718
Meyer, K.H. Chem. Ber. 1912, 45, 2843;2864
Meyer, K.H. Chem. Ber. 1914, 47, 826
Dieckmann, W. Chem. Ber. 1922, 55B, 2470
Conant, J.B.; Thompson, A.F. Jr. J. Am. Chem. Soc. 1932, 54, 4039
Ingold, C.K.; Wilson, C.L. J. Chem. Soc. 1934, 773

65
Pedersen, K.J. J. Phys. Chem. 1934, 38, 581
Bartlett, P.D.; Stauffer, C.H. J. Am. Chem. Soc. 1935, 57, 2580
Hsu, S.K.; Wilson, C.L. J. Chem. Soc. 1936, 623
Reitz, O. Z. Phys. Chem. A 1937, 179, 119
Hsu, S.K.; Ingold, C.K.; Wilson, C.L. J. Chem. Soc. 1938, 78
H2 N

OH

OH

Polce, M.J.; Wesdemiotis, C. J. Mass. Spectrom. 2000, 35, 251
Episulfonium ions (thiiranium ions)
R1
S+
R2

R5

R3

R4

Reviews:
Schmid, G.H.; Garratt, D. in The Chemistry of Double Bonded Functional Groups, (S. Patai, ed.) Wiley: New York, 1977, Chapter 9
Smit, W.A.; Zefirov, N.S.; Bodrikov, I.V.; Krimer, M.Z. Acc. Chem. Res. 1979, 12, 282
Smit, V.A.; Zefirov, N.S.; Bodrikov, I.V. in Organic Sulfur Chemistry, Invited Lecture Int. Symp., (R.K. Friedlina; A.E. Skorova, eds.) Pergamon:
Oxford, 1981, p. 159
Harring, S.R.; Edstrom, E.D.; Livinghouse, T. Adv. Heterocyclic Natural Product Synthesis 1992, 2, 299
Pasquato, L.; Destro, R.; Lucchini, V.; Modena, G. Phosphorus, Sulfur, Silicon and the related Elements 1999, 153-154, 235

66

Me2 S + BrCH 2 CH2 Br

Br-

S+

CH3 Br + CH 3 SCH 2 CH2 Br

Br

S+

Br-

S

CH3 SCH 2 CH2 Br

CH3 Br +

Cahours, A. Ann. Chem. 1865, 135, 354
Cahours, A. Ann. Chem. 1865, 136, 151
Cahours, A. Compt. Rend. 1865, 60, 620; 1174
Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267
Cl

H2 O

Cl
S

ClCH2CH 2

- Cl-

S+

Cl

OH
S

Peters, R.A.; Walker, E. Biochem. J. 1923, 17, 260
Ogston, A.G.; Holiday, E.R.; St. L. Philpot, J.; Stocken, L.A. Trans. Faraday Soc. 1948, 44, 45
Bartlett, P.D; Swain, G. J. Am. Chem. Soc. 1949, 71, 1406

Cl

H+
EtS

OH

-

Cl
EtS

OH2

+

- H2 O

Et
Et

Fuson, R.C.; Speziale, A. J. Am. Chem. Soc. 1940, 71, 1582
Fuson, R.C.; Price, C.C.; Burness, D.M. J. Org. Chem. 1946, 11, 475
Sulfenium ions

S

S+

67
R

S+

Reviews:
Parker, A.; Kharasch, N. Chem. Rev. 1959, 59, 583
Kharasch, N. in Organic Sulfur Compounds, (N. Kharasch, ed.) Pergamon Press: London, 1961, p. 375 - 396
Okuyama, T. in Chemistry of Sulfenic Acids and their Derivatives, (S. Patai, ed.) Wiley: Chichester, 1990, p. 743 - 763
NO2
S+

+ Cl-

NO2
S
Cl

100 %
H2 SO4

O2N
NO2

H
S+

O2N

Cl

HSO4 O2N

Kharasch, N.; Buess, C.M.; King, W. J. Am. Chem. Soc. 1953, 75, 6035
Robinson, E.A.; Zaidi, S.A.A. Can. J. Chem. 1966, 46, 3927
R-S-S-R + H+
R-S+ + R'-S-S-R'
R-S+ + R'-SH

R-S+ + R-SH
R-S-S-R' +

R'-S+

R-S-S-R' + H+

Benesch, R.E.; Benesch, R. J. Am. Chem. Soc. 1958, 80, 1666

68
NMe2

S+
Me

HOSO3 NMe2

Neunhöffer, O.; Nowak, A. Naturwiss. 1958, 45, 491
COOH

COOH

COOH

H2 SO4
OH
SH

S

- OHO

Ph-Br

COOH

- H+
S

Br

- H2 O

Gilman, H.; Diehl, J.W. J. Org. Chem. 1959, 24, 1914

S+
Br

S

69
X1

Ph

X2

X1

S

COOH

X

Ph

X3

X2

+ X3

S+

_

COOH

X

X2 , X3 = H, Ph
Iskander, Y.; Tewfik, R. J. Chem. Soc. 1961, 2393
Ar

Ar

S

_

R

+ R-S +

Ar

Ar

Ar = p-O2 N-C6 H4
Iskander, Y.; Riad, Y. J. Chem. Soc. 1961, 2397
SO3 -

SO3 - Ag+
O2N

NO2

O2N

SO3 -

+SCH3
O2N

NO2

NO2

N

+ CH 3 Br
- AgBr
NO2

N+
NO2

NO2

Helmkamp, G.K.; Owsley, D.C. Quart. Rep. Sulfur Chem. 1967, 2, 303
Helmkamp, G.K.; Owsley, D.C.; Barnes, W.M.; Cassey, H.N. J. Am. Chem. Soc. 1968, 90, 1635
Sulfonium Ions

SCH3

70
R2
S+
R1

R3

Reviews:
Stirling, C.J.M. in Organic Chemistry of Sulfur, (S. Oae, ed.) Plenum: New York, 1977, p. 473
Barrett, G.C. Compr. Org. Chem. 1979, 3, 105
Stirling, C.J.M. (ed.) Chemistry of the Sulphonium Group, Vol. 1, 2, Wiley: Chichester, 1981
Wilson, G.E. Jr. Tetrahedron 1982, 38, 2597
Capozzi, G.; Modena, G. Studies in Org. Chem. (Amsterdam) 1985, 19, 246
Anklam, E.; Margaretha, P. Res. Chem. Intermed. 1989, 11, 127
Ando, W.; Matsuyama, H. in Nitrogen, Oxygen, and Sulfur Ylide Chemistry, (J.S. Clark, ed.) Oxford University Press: Oxford, 2002, p. 175
Nenaidenko, V.G.; Balenkova, E.S. Russ. J. Org. Chem. 2003, 39, 291
Et2 S + Et-I
Et3 S+ Ivon Oefele, A. Ann. Chem. 1864, 132, 82
Me

I-

S+

PhCH 2 SCH 2 Ph + MeI
PhCH 2

CH2 Ph

PhCH 2 I + PhCH 2 SMe

Me

PhCH 2 SMe + MeI
Me2 S + MeI

I-

S+
PhCH 2

Me3 S+ I-

Schöller, C. Chem. Ber. 1874, 7, 1274
Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267

Me

PhCH 2 I + Me2 S

71
Et3 S+ I- + H 2 S

3 EtSH + HI

Cahours, A. Compt. Rend. 1875, 80, 1317
Cahours, A. Compt. Rend. 1875, 81, 1163
Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267
Collier, H.B.; Allen, D.E. Can. J. Res. 1942, 20B, 284
Et

CH3 NO3 + MeSEt

NO3 -

S+
Me

Me

EtNO3 + Me2 S

Me3 S+ NO3 -

Me2 S + CH 3 NO3
O2N

Me3 S+ NO3 -

+

HO

O2N

NO2

- HNO3
O2N

Me2 S+ - O

NO2

O2N

Ray, F.E.; Szasz, G.J. J. Org. Chem. 1943, 8, 121
Hughes, E.D.; Ingold, C.K.; Maw, G.A. J. Chem. Soc. 1948, 2072
Hughes, E.D.; Ingold, C.K.; Maw, G.A.; Woolf, L.I. J. Chem. Soc. 1948, 2077
Extended Cumulenones
Reviews:
Runge, W. Prog. Phys. Org. Chem. 1981, 13, 315
Propadienones (methyleneketenes)

72

R1
C

C

O

R2

Reviews:
Brown, R.F.C.; Eastwood, F.W. in The Chemistry of Ketenes, Allenes, and Related Compounds, Part 2, (S. Patai, ed.) Wiley: New York, 1980,
Chapter 19, p. 757
Brown, R.F.C.; Eastwood, F.W. Synlett 1993, 9
Gaber, A. El-A.; McNab, H. Synthesis 2001, 2059
O
O

PhNH 2
430 C

PhCH
O

PhCH=CH(CO)NHPh

PhCH=C=C=O

- CO2
- acetone

PhCH=CHCOOMe
dimerization

MeOH

O

- CO2
- CO
- acetone
PhC

O

550 C
PhCH

CHPh

CH
O

Brown, R.F.C.; Eastwood, F.W.; Harrington, K.J. Austr. J. Chem. 1974, 27, 2373

73
O
Ph

O

Ph

560 C

Ph
C

H

- CO2
- acetone

O

C

O

C

- CO

H

:

Ph

H

H

O

Brown, R.F.C.; Eastwood, F.W.; Harrington, K.J.; McMullen, G.L. Austr. J. Chem. 1974, 27, 2393
O

O
O

H

O

495 C
+

C

O

- CO2
H
- acetone

O

O

O

O

O

mCPBA

CH2 =C=C=O

C

O

O
O

COOH

O

H2 O

O

O

- acetone
O

O

O

O

O

- CO2
- acetone

O

540 C

O

CH2 =C=O

C

:

- CO

O

Brown, R.F.C.; Eastwood, F.W.; McMullen, G.L. J. Am. Chem. Soc. 1976, 98, 7421
Brown, R.F.C.; Eastwood, F.W.; McMullen, G.L. Austr. J. Chem. 1977, 30, 179

O

74

254 nm
MeOH

N

COOMe

+

C

C

COOMe

O

N

O

Mazzocchi, P.H.; Bowen, M.W.; Kachinsky, J. Chem. Commun. 1977, 53
O
O

(CH2 )n
O

FVT
(CH2 )n
- CO2
- acetone

C

C

O

O

n = 2, 3, 4, 5, 6, 10
Baxter, G.J.; Brown, R.F.C. Austr. J. Chem. 1978, 31, 327

H
Ph

Ph2 C=O + CH2 =C=C=O

Ph

O

O

O
O
CH=CH2
H

HOOC-CH=CH2 + CH 2 =C=C=O

O

Blackman, G.L.; Brown, R.D.; Brown, R.F.C.; Eastwood, F.W.; McMullen, G.L.; Robertson, M.L. Austr. J. Chem. 1978, 31, 209

75
CO + HC
N2

CH

O

O

O

C

O

650 C
- N2

O

major

O

minor

CH2 =C=C=O + CO2

O=C=C=C=O + CH2 =O

Chapman, O.L.; Miller, M.D.; Pitzenberger, S.M. J. Am. Chem. Soc. 1987, 109, 6867
R1

Br

1. SOCl2
2. [Ph3 P-N=PPh3 ]+ [Mn(CO)5 ]-

R1

R2

COOH

R2

R1

Br

R1

R2

[Ph3 P-N=PPh3 ]+ [Mn(CO)5 ]-

COCl

O

+ Mn(CO)5 Br + [Ph 3 P-N=PPh3 ]+ Cl-

C

C

O

+ Mn(CO)5 Br + [Ph 3 P-N=PPh3 ]+ Cl-

R1
O

R1

R2
C

R2

C

R2

R1 = Me, Ph, H; R2 = Me, Ph, Me

2

C

C

O
R1
O
R2

Masters, A.P.; Sorensen, T.S.; Tran, P.M. Can. J. Chem. 1987, 65, 1499

76
O

:

O

- CO2
- CO
O

CO

- CO2
O
C

:

C

C

O

77
O
O

FVP

O

- CO2
- acetone

O

FVP

O

C

C

O

- CH2 =CH 2
- CO2
- acetone

O
O

O

- CF3 COOH
O

- CH2 =CH 2
O
CF3
O

- CH2 =CH 2
O
O
C

CF3
H

C

O

- CF3 COOH

O

Brown, R.F.C.; Browne, N.R.; Coulston, K.J.; Eastwood, F.W.; Irvine, M.J.; Pullin, D.E.; Wiersum, U.E. Austr. J. Chem. 1989, 42, 1321
O
F

O

F
C

C

O

F
F

2

Brahms, J.C.; Dailey, W.P. J. Am. Chem. Soc. 1989, 111, 3071

78

O
F

FVP
O

- CO2

F

F
C

C

O

F

O

Brahms, J.C.; Dailey, W.P. J. Am. Chem. Soc. 1989, 111, 8940
R
O

R

R

FVP
O

O

- N2

+

C

C

O

R

N2

Brahms, J.C.; Dailey, W.P. Tetrahedron Lett. 1990, 31, 1381
O
S

S

O

FVT

O

- CO2
- acetone

S
C

C

O

S

O

Chuburn, F.; Lacombe, S.; Pfister-Guillouzo, G.; Chiek, A.B.; Chuche, J.; Pommelet, J.C. J. Am. Chem. Soc. 1991, 113, 1954
Butatrienones

79
R1
C

C

C

O

R2

Reviews:
None.
O
O

FVP
CH2 =C=C=C=O + CF 3 COOH

O

C
H

CF3

Brown, R.D.; Brown, R.F.C.; Eastwood, F.W.; Godfrey, P.D.; McNaughton, D. J. Am. Chem. Soc. 1979, 101, 4705
O
O

X

FVP

X

+ CO2 + Me2 C=O + CH2 =C=C=C=O

O
O

X = CH 2 , O

Brown, R.F.C.; Coulston, K.J.; Eastwood, F.W.; Gatehouse, B.M.; Guddatt, L.W.; Pfenninger, M.; Rainbow, I. Austr. J. Chem. 1984, 37, 2509

80
O

O

O

O

- H2 O
COOH

C

C

- CO
- CH2 =O

C

C

O

C
H

O

C

C

C

C

O

- H2 O
COOH
Brown, R.F.C.; Coulston, K.J.; Eastwood, F.W.; Irvine, M.J. Austr. J. Chem. 1991, 44, 87

O

O

Cevasco, G.; Pardini, R.; Thea, S. Eur. J. Org. Chem. 1998, 665
Heterocumulenones (iminopropadienones)
Reviews:
Wentrup, C.; Kappe, C.O.; Wong, M.W. Pure Appl. Chem. 1995, 67, 749
Yranzo, G.I.; Elguero, J.; Flammang, R.; Wentrup, C. Eur. J. Org. Chem. 2001, 2209
R

O

O
NH

N
O

FVP

FVP

RNH

O

R1

O

R-N=C=C=C=O

N

O

R = Me, Ph; R1 = MeS, Me2 N

81
Mosandl, T.; Kappe, C.O.; Flammang, R.; Wentrup, C. Chem. Commun. 1992, 1571
Mosandl, T.; Stadtmuller, S.; Wong, M.W.; Wentrup, C. J. Phys. Chem. 1994, 98, 1080
Kappe, C.O.; Flammang, R.; Wentrup, C. Heterocycles 1994, 37, 1615
O

O
RNH

O

O

FVT
RN

X

RN=C=C=C=O

C

- HX

O

O

- CO2
- acetone

O

O

- CO2
- acetone

FVT
O

RN

C

R = Ph, iPr, tBu
X = SMe, NMe2 , OMe, tBu-NH

RN

[1,3]-X

C

X

O

X

Moloney, D.W.J.; Wong, M.W.; Flammang, R.; Wentrup, C. J. Org. Chem. 1997, 62, 4240
N

X

FVP
N
N

N=C=C=C=O

O

X = SMe, Cl, NMe 2 , NEt 2 , OMe
Plug, C.; Frank, W.; Wentrup, C. J. Chem. Soc. Perkin Trans. 2 1999, 1087

82
O
Ar-NH

O

R1

O
O

_
NHAr

N

N-Ar

N+

R-N=C=C=C=O
N

N

O

N
O

Ar

O
NH

N
O

N

Shtaiwi, M.; Wentrup, C. J. Org. Chem. 2002, 67, 8558
Halonium Ions
R1

X

+

R4

X = Cl, Br, I
R2

N

R3

Reviews:
Sandin, R.B. Chem. Rev. 1943, 32, 249
Banks, D.F. Chem. Rev. 1966, 66, 243
Crist, D.R.; Leonard, N.J. Angew. Chem. Int. Ed. 1969, 8, 962
Peterson, P.E. Acc. Chem. Res. 1971, 4, 407
Olah, G.A. Aldrichimica Acta 1973, 6, 7

83
Olah, G.A. Halonium Ions, Wiley-Interscience: New York, 1975
Grushin, V.V. Acc. Chem. Res. 1992, 25, 529
Ruasse, F. Adv. Phys. Org. Chem. 1993, 28, 207
Koser, G.F. in The Chemistry of Halides, Pseudo-Halides, Azides (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1983, Vol. 2, p. 1265
Koser, G.F. in The Chemistry of Halides, Pseudo-Halides, Azides (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1995, Vol. 2, p. 1173
Br+

HOOC

COOH

HOOC

COOH

COOH
Br+

Br2
HOOC

Br

Br-

Br2

HOOC
Br

COOH

COOH

Br

HOOC

Br

Br

COOH

COOH

Br-

HOOC

HOOC

Br

McKenzie, A. Proc. Chem. Soc. 1911, 27, 150
McKenzie, A. J. Chem. Soc. 1912, 101, 1196
Frankland, P.F. J. Chem. Soc. 1912, 101, 673
Kuhn, R.; Wagner-Jauregg, T. Chem. Ber. 1928, 61, 519

COOH

Cl

I+

ICl
CH3 CH

CHCOOH

I

ClCOOH

Ingold, C.K.; Smith, H.G. J. Chem. Soc. 1931, 2742
Roberts, I.; Kimball, G.E. J. Am. Chem. Soc. 1937, 59, 947

84

Ph

Br

Br+

Br2
- Br-

Br

MeOH

+
Ph

Ph

Ph
MeO

Br

+

Br

OMe

Ph

Ph

major
Bartlett, P.D.; Tarbell, D.S. J. Am. Chem. Soc. 1936, 58, 466
COO - OOC

Cl2

Cl+
- OOC

Cl

- ClCOO -

COO -

O
O

Tarbell, D.S.; Bartlett, P.D. J. Am. Chem. Soc. 1937, 59, 407
Lucas, H.J.; Winstein, S. J. Am. Chem. Soc. 1939, 61, 1576; 2845
Lucas, H.J.; Garner, H.K. J. Am. Chem. Soc. 1950, 72, 2145
Lucas, H.J.; Gould, C.W. Jr. J. Am. Chem. Soc. 1941, 63, 2541
Barton, D.H.R.; Miller, E.; Young, H.T. J. Chem. Soc. 1951, 2698
Lemieux, R.U.; Fraser-Reid, B. Can. J. Chem. 1965, 43, 1458
Olah, G.A.; Bollinger, J.M. J. Am. Chem. Soc. 1967, 89, 4744
Cl+

I-

Br+

Cl-

85

Sandin, R.B.; Hay, A.S. J. Am. Chem. Soc. 1952, 74, 274 (first stable bromonium and chloronium salts)
Hydronium ions
H
O
H

+
H

Reviews:
Williams, J.H. in Hydrogen Bond (P. Schuster, G. Zundel, C. Sandorfy, eds.) North-Holland: Amsterdam, 1976, Vol. 2, p. 655
Lundgren, J.O.; Olovsson, I. in Hydrogen Bond (P. Schuster, G. Zundel, C. Sandorfy, eds.) North-Holland: Amsterdam, 1976, Vol. 2, p. 471
Giguere, P.A. J. Chem. Educ. 1979, 56, 571
H3 O+ Br-

H2 O + HBr

(SO2 solvent)

Bagster, L.S.; Cooling, G. J. Chem. Soc. 1920, 117, 693
H3 O+ ClO4 -

H3 O+ NO3 -

H3 O+ HBF 3 -

Volmer, M. Ann. Chem. 1924, 440, 200
Klinkenberg, L.J.; Ketelaar, J.A.A. Rec. Trav. Chim. 1935, 54, 959
Richards, R.E.; Smith, J.A.S. Trans. Faraday Soc. 1951, 47, 1261
Kakiuchi, H.; Shono, H.; Komatsu, K.; Kigoshi, K. J. Chem. Phys. 1951, 19, 1069
Bethell, D.E.; Sheppard, N. J. Chem. Phys. 1953, 21, 1421
Iminium Ions
R1

R4

+ N
R2

R3

86
Reviews:
Paukstelis, J.V. in Enamines: synthesis, structure, and reactivity (G. Stork, ed.) Marcel Dekker: New York, 1969, p. 169
Pihlaja, K. in The Chemistry of Amidines, Imidates (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1991, Vol. 2, p. 323
Stewart, T.D.; Bradley, W.E. J. Am. Chem. Soc. 1932, 54, 4172
Julg, A.; Carles, P. Compt. Rend. 1960, 251, 1782
Janovsky complex
Reviews:
None.
H
O

O2N

NaX

O

O2N

+

_

- HX

R

NO2

R

Na+

NO2

Janovsky, J.V. Chem. Ber. 1886, 19, 2155
Ketenes
R1
C

C

O

R2

Reviews:
Staudinger, H. Die Ketene, Verlag Enke: Stuttgart, 1912
Patai, S. (ed.) The Chemistry of Ketenes, Allenes, and Related Compounds, Wiley: Chichester, 1980
Dötz, K.H.; Fuengen-Koester, B. Chem. Ber. 1980, 113, 1449
Tidwell, T.T. Ketenes, Wiley: New York, 1995
Kollenz, G.; Heilmayer, W.; Kappe, C.O.; Wallfisch, B.; Wentrup, C. Croatica Chem. Acta 2001, 74, 815

87
Kirmse, W. Eur. J. Org. Chem. 2002, 2193
Singh, G.S.; Mdee, L.K. Curr. Org. Chem. 2003, 7, 1821
O

O

R1

R2
R1

- N2

C

:

R2

R1

hν or ∆

R2

N2

O
Ph

Zn

Ph
Cl
Cl
Ph

C

- ZnCl2

C

O

Ph

Staudinger, H. Chem. Ber. 1905, 38, 1735
Staudinger, H. Chem. Ber. 1907, 40, 1145
Staudinger, H. Ann. Chem. 1908, 356, 51
Wilsmore, N.T.M. Proc. Chem. Soc. 1908, 23, 229
Wilsmore, N.T.M. J. Chem. Soc. 1908, 91-92, 1938
Collie, J.N. Proc. Chem. Soc. 1908, 23, 280
Wilsmore, N.T.M.; Stewart, A.W. Proc. Chem. Soc. 1908, 23, 309
Collie, J.N. J. Chem. Soc. 1908, 91-92, 1806
Smith, L.I.; Hoehn, H.H. Org. Synth. Coll. Vol. 1955, 3, 356
Taylor, E.C.; McKillop, A.; Hawks, G.H. Org. Synth. 1972, 52, 36
Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 594
Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 906
Wilsmore, N.T.M.; Stewart, A.W. Chem. Ber. 1908, 41, 1025
Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 1516
Staudinger, H. Chem. Ber. 1908, 41, 1355

C

O

88
Staudinger, H. Chem. Ber. 1908, 41, 1493
Staudinger, H.; Ott, E. Chem. Ber. 1908, 41, 2208
Schroeter, G. Chem. Ber. 1909, 42, 2336
Staudinger, H.; Kubinsky, J. Chem. Ber. 1909, 42, 4213
Staudinger, H.; Bereza, S. Chem. Ber. 1909, 42, 4908
Staudinger, H.; Klever, H.W.; Kober, P. Ann. Chem. 1910, 374, 1
Leuchs, H.; Theodorescu, G. Chem. Ber. 1910, 43, 1239
Schmidlin, J.; Bergman, M. Chem. Ber. 1910, 43, 2821
Schmidlin, J.; Huber, M. Chem. Ber. 1910, 43, 2824
Staudinger, H.; Jelagin, S. Chem. Ber. 1911, 44, 365
Staudinger, H. Chem. Ber. 1911, 44, 521; 533; 543
Staudinger, H.; Bereza, S. Ann. Chem. 1911, 380, 243
Staudinger, H.; Ruzicka, L. Ann. Chem. 1911, 380, 278
Staudinger, H. Chem. Ber. 1911, 44, 1619
Staudinger, H.; Ott, E. Chem. Ber. 1911, 44, 1631
Staudinger, H.; Kupfer, O. Chem. Ber. 1911, 44, 1638; 2194
Staudinger, H.; Kon, N. Ann. Chem. 1912, 384, 38
Staudinger, H. Ann. Chem. 1912, 387, 254
Staudinger, H.; Kupfer, O. Chem. Ber. 1912, 45, 501
Staudinger, H. Z. Angew. Chem. 1914, 27, 354
Staudinger, H.; Gohring, O.; Scholler, M. Chem. Ber. 1914, 47, 40
Staudinger, H.; Maier, J. Ann. Chem. 1914, 401, 292
Staudinger, H.; Hirzel, H. Chem. Ber. 1916, 49, 2522

O



..

H
O
O

H

89
O

O

H

H


RO

RO

Quinkert, G.; Wegemund, B.; Blanke, E. Tetrahedron Lett. 1962, 221
O
O


CHCl2

CHCl2

Cl

Cl

O



O
Cl

Cl
Cl

Cl

Cl

Cl

Chapman, O.L.; Lassila, J.D. J. Am. Chem. Soc. 1968, 90, 2449
Metal Ketenides
M
C
M

Reviews:
None.

C

O

90
O

O

O
Ag

+

2

O

pyridine

O- Ag+

C

O

C

O

+ 3
OH

Ag

Blues, E.T.; Bryce-Smith, D.; Hirsch, H.; Simons, M.J. J. Chem. Soc. D 1970, 699
Bryce-Smith, D.; Blues, E.T. DE 2,047,373 (1971)
Bryce-Smith, D. Chem. Ind. 1975, 154
Cu
C

C

O

Cu

Blues, E.T.; Bryce-Smith, D.; Kettlewell, B.; Roy, M. Chem. Commun. 1973, 921
Au
C

C

O

Au

Blues, E.T.; Bryce-Smith, D.; Lawston, I.W.; Wall, G.D. Chem. Commun. 1974, 513
Ketene zwitterions
R1

O-

R2

N

+

R1

O-

R2

N+
R3

R4

R5

R1

O-

R2

P+
R3

R4

R5

R1

O-

R2

S+
R3

R4

91
Reviews:
None.
EtOOC

EtOOC
C

C

+

O

R

R

EtOOC

N+
EtOOC

N

_
O

Gompper, R.; Wolf, U. Ann. Chem. 1979, 1388
O
O

N2

NH

C

-O
C
+



N

N
+

NH

- N2

Pacansky, J.; Chang, J.S.; Brown, D.W.; Schwarz, W. J. Org. Chem. 1982, 47, 2233

O

-O

N+
C

C

+
- O3S

N

- O3S

Barra, M.; Fisher, T.A.; Cenigliaro, G.J.; Sinta, R.; Scaiano, J.C. J. Am. Chem. Soc. 1992, 114, 2630

92

Ketyl Radicals and Ketyl Radical Ions

R1

OH

O-

.

.

R2

R1

+ H+
R2

Reviews:
Michaelis, L. Chem. Rev. 1935, 16, 243
Holy, N.L.; Marcum, J.D. Angew. Chem. Int. Ed. 1971, 10, 115
Netto-Ferreira, J.C.; Scaiano, J.C. Res. Chem. Intermediates 1989, 12, 187
O

O - Na+

Na or
Mg-MgI2

Ar

Ar

Ar
O-

O
Ar
Ar
O

.

Na+ - O
Ar

Ar

Ar

Ar
Ar

K+

O- Na+

KOH

Ar
Ar
O

.

Laurent, A. Ann. Chim. Phys. 1835, 59, 367
Laurent, A. Ann. Chim. Phys. 1836, 17, 89; 91
Liebermann, C.; Homeyer, J. Chem. Ber. 1879, 12, 1971
Bamberger, E. Chem. Ber. 1885, 18, 865
Beckmann, E. Chem. Ber. 1889, 22, 912
Beckmann, E.; Paul, T. Ann. Chem. 1891, 266, 1
Schlenk, W.; Weichel, T. Chem. Ber. 1911, 44, 1182
Schlenk, W.; Thal, A. Chem. Ber. 1913, 46, 2840
Schlenk, W.; Appenrodt, J.; Michael, A.; Thal, A. Chem. Ber. 1914, 47, 473

93

O

O
O-

O

KOH/
EtOH

O
O

O
O

O

K+

O

.

OH

Fischer, E. Ann. Chem. 1882, 211, 314
Weitz, E.; Schwechten, H.W. Chem. Ber. 1926, 59, 2307
Weitz, E.; Schwechten, H.W. Chem. Ber. 1927, 60, 545; 1203
Hantzsch, A. Chem. Ber. 1921, 54B, 1267
O

O
Ph

Ph

O - K+

+

Ph
Ph

O

KOH
2

Ph
Ph

OH

Scholl, R. Chem. Ber. 1899, 32, 1809
Scholl, R.; Hahle, H. Chem. Ber. 1923, 56B, 918

O

.

O

94
O

O - [MgBr]+

+ Ph 3 C-MgBr
Ar

Ar

Ar

O - [MgBr]+

2
Ar

.

.

+ Ph 3 C
Ar

O - [MgBr]+
Ar
Ar

Ar

Ar
Ar
[BrMg]+ - O

Gomberg, M.; Bachmann, W.E. J. Am. Chem. Soc. 1927, 49, 236
Bachmann, W.E. J. Am. Chem. Soc. 1931, 53, 2758
Bachmann, W.E. J. Am. Chem. Soc. 1933, 55, 770
Bachmann, W.E. J. Am. Chem. Soc. 1933, 55, 1179
Arbuzov, A.E.; Arbuzova, I.A. J. Gen. Chem. USSR 1932, 2, 388
Nazarov, N. Compt. Rend. Acad. Sci. URSS 1934, 1, 123
Nazarov, N. Compt. Rend. Acad. Sci. URSS 1934, 1, 325
magnetic susceptibility measurements:
Sugden, S. Trans. Faraday Soc. 1934, 30, 18
Wooster, C.R.; Dean, J.G. J. Chem. Soc. 1935, 57, 112
Müller, E.; Teschner, F. Ann. Chem. 1936, 525, 1
Anschutz, L. Chem. Ber. 1938, 71B, 1902
Müller, E.; Wiesemann, W. Chem. Ber. 1936, 69, 2156
Müller, E. Ann. Chem. 1938, 537, 86
Müller, E. Angew. Chem. 1938, 51, 657
Müller, E.; Janke, W. Z. Elektrochem. 1939, 45, 380
Bowden, S.T.; John, T. J. Chem. Soc. 1940, 213
Meisenheimer-Jackson Complexes

.

95
R1

R2

O2N

R1

_

R2

NO2 O2N

R1
NO2 O2N

R2
NO2

_

_
NO2

R1

R2

O2N

NO2

ON+

R1

NO2

O2N

NO2
-O

O-

NO2

O-

R2

+

R2

N

NO2

+

NO2

N
-O

R1

O-

Reviews:
Huisgen, R.; Sauer, J. Angew. Chem. 1960, 72, 91
Huisgen, R.; Sauer, J. Angew. Chem. 1960, 72, 294
Ross, S.D. Prog. Phys. Org. Chem. 1963, 1, 31
Crampton, M.R. Adv. Phys. Org. Chem. 1969, 7, 211

96
O
H
O2N

NO2

NO2

Na2 SO3

O2N

OS

-

O
NO2

2 Na+

NO2

Jackson, C.L.; Robinson, W.S. Am. Chem. J. 1889, 11, 93
Jackson, C.L.; Gazzolo, F.H. Am. Chem. J. 1900, 23, 376
Jackson, C.L.; Earle, R.B. Am. Chem. J. 1903, 29, 89
Meisenheimer, J., Ann. Chem. 1902, 323, 205
Servis, K. J. Am. Chem. Soc. 1965, 87, 5495 (NMR studies)
Mercurinium ions
OAc
Hg+
R1
R2

R4
R3

Reviews:
Zefirov, N.S. Usp. Khim. 1965, 34, 1272
Zefirov, N.S. Russ. Chem. Rev. 1965, 34, 527
Chatt, J. Chem. Rev. 1951, 48, 7
Kitching, W. Organometallic Chem. Rev. 1968, 3, 61

97

+ Hg +2

Hg+2

+ Hg +2 + H 2 O

Hg+

OH

+ H+

Lucas, H.J.; Hepner, F.R.; Winstein, S. J. Am. Chem. Soc. 1939, 61, 3102
OAc

Hg(OAc)2

Hg+

OAc

-

HgOAc

R

H2 O

- OAc-

- HOAc

R

HgOAc

R

AcO

- Hg
HO
- B(OH)3
- NaOAc

HO

R

Brook, A.G.; Wright, G.F. Can. J. Res. 1950, 28B, 623
Wright, G.F. Chemistry in Canada 1950, 2(9), 29
Wright, G.F. Ann. N.Y. Acad. Sci. 1957, 65, 436
Abercrombie, M.J.; Rodgman, A.; Bharucha, K.R.; Wright, G.F. Can. J. Chem. 1959, 37, 1328
HgX 2
ROH

Hg+

X

R

NaBH4

X

HgX

-

OR

98

Traylor, T.G.; Baker, A.W. J. Am. Chem. Soc. 1963, 85, 2746
H
MeO

MeO+

H+

I-

- MeOH

CH2
HgI

+ HgI 2

+ HgI

HgI

I-

CH2

IH

MeO

H+

MeO+

- MeOH
CH2

_ HgI
2

+ HgI 2

HgI 2

_ HgI 2

I-

CH2

IH

MeO

H+

MeO+

- I-

- MeOH

CH2

_ HgI 3

_ HgI 3

CH2

_ HgI
3

Kreevoy, M.M.; Stokker, G.; Kretchmer, R.A.; Ahmed, A.K. J. Org. Chem. 1963, 28, 3184
Ichikawa, K.; Nishimura, N.; Takayama, S. J. Org. Chem. 1965, 30, 1593

+ HgI 2

99
OAc
Hg+
PhCH 2CH

CH2

OAc-

+ Hg(OAc)2
PhCH 2

AcO

HgOAc

PhCH 2

Wolfe, S.; Campbell, P.G.C. Tetrahedron Lett. 1966, 4203
Treibs, W.; Lucius, G.; Hogler, H.; Breslauer, H. Ann. Chem. 1953, 581, 59
Treibs, W.; Bast, H. Ann. Chem. 1949, 561, 165
X
HgX

Hg+

HgX 2
C

H+

ROH
C

- X-

- H+
RO

H

H

+
HgX

- HgX +
RO

RO

100
Waters, W.L.; Kiefer, E.F. J. Am. Chem. Soc. 1967, 89, 6261
Bach, R.D. Tetrahedron Lett. 1968, 5841
Bach, R.D. J. Am. Chem. Soc. 1969, 91, 1771
Metal carbenoids
+
MLn

MLn

:

_
R1

R1

R2

R2

Reviews:
Koebrich, G. Angew. Chem. Int. Ed. 1972, 11, 473
Wulfman, D.S.; Poling, B. Reactive Intermediates 1980, 1, 321
Miller, D.J.; Moody, C.J. Tetrahedron 1995, 51, 10811
Bruce, M.I. Chem. Rev. 1998, 98, 2797

Cu

Ph

- N2

O

O

ROH
Ph

Ph

:

O

H

N2

Cu
Yates, P. J. Am. Chem. Soc. 1952, 74, 5376

OR

101
Li

R-Li + CH2 Cl2

H

R-H +
Cl

Cl

Cl

Li

Cl

RCH=CH 2

:

H
Cl

- LiCl

Cl

H
R

Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1960, 82, 5723
Closs, G.L.; Schwartz, G.M. J. Am. Chem. Soc. 1960, 82, 5729
Closs, G.L.; Moss, R.A.; Coyle, J.J. J. Am. Chem. Soc. 1962, 84, 4985 (sterics)
Closs, G.L. J. Am. Chem. Soc. 1962, 84, 809
Closs, G.L.; Moss, R.A. J. Am. Chem. Soc. 1964, 86, 4042

:

Cl

Cl

H

Li

:

Li

- LiCl

Cl

H

- LiCl

Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1961, 83, 1003
Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1961, 83, 2015

102
Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1963, 85, 99

:

O- Li+

MeLi + CH2 Cl2

- LiCl Cl
- Me-H

Cl

O- Li+

O- Li+
O

Ph-O- Li+
H

Cl

- LiCl

Cl

Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1961, 83, 599
MeLi
- LiCl
Cl

Cl

Ph

Cl

- Me-H

Ph

Li

LiCl

Cl

- LiCl

Me

MeLi

:

MeLi

Ph

Cl

Ph

Nicholas cation

MeLi

Li

Cl

- LiCl Ph

Me

- LiCl

- LiCl

Closs, G.L.; Coyle, J.J. J. Org. Chem. 1966, 31, 2759

Ph

Me
Li

Cl

- MeLi
Ph

Me

103
R2

+
R1

R3

(CO) 3Co

Co(CO)3

Reviews:
Nicholas, K.M. Acc. Chem. Res. 1987, 20, 207
R2
R2
R1

Co2 (CO)8 R1

OH

R3

- 2 CO

R3

(CO) 3Co

R2

OH

Co(CO)3

R2

+
H+
- H2 O

R1

(CO) 3Co

R3

Co(CO)3

Nu-

R1

(CO) 3Co

R

:
singlet

..

:

:

Nitrenes
N

R3

[O]

Nicholas, K.M.; Pettit, R. Tetrahedron Lett. 1971, 37, 3475
Nicholas, K.M.; Pettit, R. J. Organometallic Chem. 1972, 44, C21
Connor, R.E.; Nicholas, K.M. J. Organometallic Chem. 1977, 125, C45

R

Nu

N

triplet

Reviews:
Kirmse, W. Angew. Chem. 1959, 71, 540
Horner, L.; Christmann, A. Angew. Chem. 1963, 75, 707
Abramovitch, R.A.; Davis, B.A. Chem. Rev. 1964, 64, 149
Lwowski, W. Angew. Chem. Int. Ed. 1967, 6, 897
Gilcrist, T.L.; Rees, C.W. Carbenes, Nitrenes, and Arynes, Appleton-Century Crofts: New York, 1969
Lwowski, W. (ed.) Nitrenes, Wiley: New York, 1970
Abramovitch, R.A. Chem. Soc. Spec. Publ. 1970, 24, 323

Co(CO)3

R2
R1

Nu
R3

104
Abramovitch, R.A.; Sutherland, R.G. Forsch. Chem. Forsch. 1970, 16, 1
Wasserman, E. Prog. Phys. Org. Chem. 1971, 8, 319
Abramovitch, R.A. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 127
Tomioka, H. Bull. Chem. Soc. Jpn 1998, 71, 1501
Gritsan, N.P.; Platz, M.S. Adv. Phys. Org. Chem. 2001, 36, 255
O

O

O
R

R

NH

- HBr

: :

Br
R

R'OH
N

N

C

O

RNH

O
O
R1

R2

NH

+ H2O

R1 NH 2 + CO2 + R2 COOH

O

Lossen, W., Ann. Chem. 1872, 161, 347 (Lossen rearrangement)
Tiemann, F. Chem. Ber. 1891, 24, 4162 (first proposed as transients in Lossen rearrangement)
Lengfeld, F.; Stieglitz, J. Am. Chem. J. 1893, 15, 215
Stieglitz, J. Am. Chem. J. 1896, 18, 751
Stieglitz, J. Am. Chem. J. 1903, 29, 49
H
N
Ph3 C

X

- HX

Ph3 C

: :

Ph
N

N

Morgan, A.F. J. Am. Chem. Soc. 1916, 38, 2095
Vosburgh, I. J. Am. Chem. Soc. 1916, 38, 2081
Stagner, B.A. J. Am. Chem. Soc. 1916, 38, 2069

Ph

Ph

OR'

105
Staudinger, H.; Miescher, K. Arch. Sci. Phys. Nat. 1917, 44, 387
Staudinger, H.; Miescher, K. Helv. Chim. Acta 1919, 2, 554
Curtius, T.; Schmidt, F. Chem. Ber. 1922, 55, 1571
Curtius, T. Z. Angew. Chem. 1913, 26(3), 134
Bertho, A. J. Prakt. Chem. 1928, 120[2], 89
Taylor, T.W.J.; Owen, J.S.; Whittaker, D. J. Chem. Soc. 1938, 206
Dinitrenes
N

:

..

:

..

X

N

quintet

N

N

N

: :

- 2 N2

: :

N3

: :


N3

: :

Reviews:
Nimura, S.; Yabe, A. in Magnetic Properties of Organic Materials, (P.M. Lahti, ed.) Marcel Dekker: New York, 1999, Chapter 7, p. 127

N

N


N3

- 2 N2

: :

N3

: :

Trozzolo, A.M.; Murray, R.W.; Smolinsky, G.; Yager, W.A.; Wasserman, E. J. Am. Chem. Soc. 1963, 85, 2526

N

Hall, J.H. J. Am. Chem. Soc. 1965, 87, 1147

CN
CN

106



..

..

N

N

:

N3

:

N3

- 2 N2
Wasserman, E.; Murray, R.W.; Yager, W.A.; Trozzolo, A.M.; Smolinsky, G. J. Am. Chem. Soc. 1967, 89, 5076 (first quintet nitrene observed)
Chapyshev, S.V.; Tomioka, H. Bull. Chem. Soc. Jpn 2003, 76, 2075
Trinitrenes

:

..

N

..

:

:

..

N

X

N

septet
Reviews:
None.

..

N3
NC

..

N

CN

N

NC

CN

N3

N3


N3

N3
CN

77 K
- N2

CN

- 2 N2

NC

CN

..

..

N

N

CN

Wasserman, E.; Schueller, K.; Yager, W.A. Chem. Phys. Lett. 1968, 2, 259
Chapyshev, S.V.; Walton, R.; Sanborn, J.A.; Lahti, P.M. J. Am. Chem. Soc. 2000, 122, 1580

107
Chapyshev, S.V.; Kuhn, A.; Wong, M.; Wentrup, C. J. Am. Chem. Soc. 2000, 122, 1572
Chapyshev, S.V. Mendeleev Commun. 2002, 168
Oda, N.; Nakai, T.; Sato, K.; Shiomi, D.; Kozaki, M.; Okada, K.; Takui, T. Synth. Met. 2001, 121, 1840
N3

N

N

N

N3

..

..

..







- N2

- N2

- N2

N3

N3

N3

..
N

N3

..

..

N

HCN + NC-N=C=N-CN

N

Sato, T.; Narazaki, A.; Kawaguchi, Y.; Niino, H.; Bucher, G. Angew. Chem. Int. Ed. 2003, 42, 5206
Sato, T.; Narazaki, A.; Kawaguchi, Y.; Niino, H.; Bucher, G.; Grote, D.; Wolff, J.J.; Wenk, H.H.; Sander, W.W. J. Am. Chem. Soc. 2004, 126,
7846

:

Nitrenium Ions
N
R1

+

R2

Reviews:
Gassman, P.G. Acc. Chem. Res. 1970, 3, 26
Abramovitch, R.A.; Jerayaman, R. in Azides and Nitrenes: reactivity and utility, (E.F.V. Scriven, ed.) Academic Press: Orlando, FL, 1984, p.
297
Simonova, T.P.; Nefedov, V.D.; Toropova, M.A.; Kirillov, N.F. Russ. Chem. Rev. 1992, 61, 584
McClelland, R.A. Tetrahedron 1996, 52, 6823
Novak, M.; Rajagopal, S. Adv. Phys. Org. Chem. 2001, 36, 167
+ OH2

OH

N
R

Ph3 C

:

Ph3 C

:

N

N
R

- H2 O

Ph3 C

:

H

Ph

+

+

H2 O

N+
R

Ph2 C

R

Ph2 C=O + Ph-NHR

108

Cl

Ph

+
N
R

- Cl-

Ph3 C

H2 O

N+

:

Ph3 C

:

N

R

Ph2 C

Ph2 C=O + Ph-NHR

R

Stieglitz, J.; Leech, P.N. Chem. Ber. 1913, 46, 2147
Stieglitz, J.; Leech, P.N. J. Am. Chem. Soc. 1914, 36, 272
Stieglitz, J.; Stagner, B.A. J. Am. Chem. Soc. 1916, 38, 2046
Heller, H.E.; Hughes, E.D.; Ingold, C.K. Nature 1951, 168, 909 (first kinetic evidence)

MeOH

NaOCl
N

NH

Cl

- Cl-

+

N

+

N

N
MeO

Gassman, P.G.; Fox, B.L. Chem. Commun. 1966, 153
Gassman, P.G.; Fox, B.L. J. Am. Chem. Soc. 1967, 89, 338

MeOH

N

N
Cl

+

+

MeO

N

Cl

N

N

Cl-

109
Gassman, P.G.; Cryberg, R.L. J. Am. Chem. Soc. 1968, 90, 1355
Gassman, P.G.; Cryberg, R.L. J. Am. Chem. Soc. 1969, 91, 2047; 5176
Ac

OSO3 -

Ac

N

Ac
N

SO4 -2

HI
I- I2
- SO4 -2

+
Y

H
N

Y

Y

Pelecanou, M.; Novak, M. J. Am. Chem. Soc. 1985, 107, 4499
Fishbein, J.C.; McClelland, R.A. J. Am. Chem. Soc. 1987, 109, 2824
Novak, M.; Kahley, M.J.; Lin, J.; Kennedy, S.A.; Swanegan, L.A. J. Am. Chem. Soc. 1994, 116, 11626
Novak, M.; Kennedy, S.A. J. Am. Chem. Soc. 1995, 117, 574
Novak, M.; Kahley, M.J.; Lin, J.; Kennedy, S.A.; James, T.J. J. Org. Chem. 1995, 60, 8294
McClelland, R.A.; Davidse, P.A.; Hadzialic, G. J. Am. Chem. Soc. 1995, 117, 4173
O

O

O
O
N

SO3 -

N+

+

- SO4 -2
Ph

N

Ph

Ph

Novak, M.; Kahley, M.J.; Eiger, E.; Helmick, J.S.; Peters, H.E. J. Am. Chem. Soc. 1993, 115, 9453

110
Novak, M.; Lin, J. J. Org. Chem. 1999, 64, 6032
Nitrilium Ions
+
R1

N

C

R2

Reviews:
Hegarty, A.F. Acc. Chem. Res. 1980, 13, 448
O

N

R1

R2

OH

OH

P2 O5

N

O
P
O

R2

R1

O
P

O
P

O

O

O

N
OH
O

R1

O

O

P

P

O

O

- P2 O5

R2
R1

OH

R1

Beckmann, E., Chem. Ber. 1886, 19, 988 (Beckmann rearrangement)
Klages, F.; Grill, W. Ann. Chem. 1956, 594, 21
Ugi, I.; Beck, F.; Fetzer, U. Chem. Ber. 1962, 95, 126
Hassner, A.; Levy, L.A.; Gault, R. Tetrahedron Lett. 1966, 27, 3119
Nitronium Ions
+
O

N

Reviews:

O

O

P

R1

R2

N

-O

O

R2

R2

OH
N+

NH

111
Ridd, J.H. Studies in Chemical Structure and Reactivity 1966, 133
Stock, L.M. Prog. Phys. Org. Chem. 1976, 12, 21
Ridd, J.H. Adv. Phys. Org. Chem. 1978, 16, 1
Olah, G.A. Acc. Chem. Res. 1980, 13, 330
Olah, G.A.; Narang, S.C.; Olah, J.A.; Lammertsma, K. Proc. Natl. Acad. Sci. USA 1982, 79, 4487
Ridd, J.H. Chem. Soc. Rev. 1991, 20, 149
Eberson, L.; Hartshorn, M.P.; Radner, F. Acta Chem. Scand. 1994, 48, 937
Lauer, K.; Oda, R. J. Prakt. Chem. 1937, 148, 287
Hughes, E.D.; Ingold, C.K.; Reed, R.I. Nature 1946, 158, 448
Gillespie, R.J.; Graham, J.; Hughes, E.D.; Ingold, C.K.; Peeling, E.R.A. Nature 1946, 158, 480
Ingold, C.K.; Millen, D.J.; Poole, H.G. Nature 1946, 158, 480
Goddard, D.R.; Hughes, E.D.; Ingold, C.K. Nature 1946, 158, 480
Titov, A.I. J. Gen. Chem. USSR 1947, 17, 382
Nitrosonium Ions
+

:N

O

Reviews:
Kreher, R. Angew. Chem. Int. Ed. 1973, 12, 1022
Mocella, M.T.; Okamoto, M.S.; Barefield, E.K. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry 1974, 4, 69
Ridd, J.H. Adv. Phys. Org. Chem. 1978, 16, 1
Olah, G.A. Acc. Chem. Res. 1980, 13, 330
Williams, D.L.H. Adv. Phys. Org. Chem. 1983, 19, 381
Bobbitt, J.M.; Flores, M.G.L. Heterocycles 1988, 27, 509
Blackall, E.L.; Hughes, E.D.; Ingold, C.K. J. Chem. Soc. 1952, 28
Deschamps, J. Mem. Services Chim. Etat (Paris) 1953, 38, 335
Lang, F.M. Chim. Industrie 1954, 71, 913
Lewis, J.; Wilkins, R.G. Chem. Ind. 1954, 634
Szabo, Z.G.; Bartha, L.G.; Lakatos, B. J. Chem. Soc. 1956, 1784
Bayliss, N.S.; Watts, D.W. Austral. J. Chem. 1956, 9, 319
Beattie, I.R. . J. Chem. Soc. 1957, 367

112
Sharp, D.W.A.; Thorley, J. J. Chem. Soc. 1963, 3557 (IR spectrum of nitrosonium ion)
Non-classical ions (hypercoordinate carbocations, sigma-bridged cations)
I

II

I

[1,6-H]
+

BsO

1
2

-

- OBs
6

AcO

1

+

+

2

6

[1,2-H]

HOAc

III

+

+

[1,6-H]

HOAc
[1,6-H]

OBs

1
6

OAc

+

- OBs-

+

2
II

1

+
I

6
II

Reviews:
Winstein, S. Quart. Rev. (London) 1969, 23, 1411
Bartlett, P.D. Non-classical Ions: reprints and commentary, W.A. Benjamin, Inc.: New York, 1965
Kramer, G.M. Adv. Phys. Org. Chem. 1975, 11, 177
Brown, H.C. The Non-classical Ion Problem, Plenum Press: New York, 1977

2

113
Brown, H.C. Top. Curr. Chem. 1979, 80, 1
Saltzman, M.D.; Wilson, C.L. J. Chem. Educ. 1980, 57, 289 (non-classical name)
Brown, H.C. Acc. Chem. Res. 1983, 16, 432
Olah, G. Acc. Chem. Res. 1983, 16, 440
Walling, C. Acc. Chem. Res. 1983, 16, 448
Nevell, T.P.; de Salas, E.; Wilson, C.L. J. Chem. Soc. 1939, 1188 (first suggestion of bridged carbocations)
Winstein, S.; Trifan, D. J. Am. Chem. Soc. 1949, 71, 2953
Winstein, S.; Morse, B.K.; Grunwald, E.; Jones, H.W.; Corse, J.; Trifan, D.; Marshall, H. J. Am. Chem. Soc. 1952, 74, 1127
Winstein, S.; Trifan, D. J. Am. Chem. Soc. 1952, 74, 1147; 1154
Olah, G.A.; White, A.M. J. Am. Chem. Soc. 1969, 91, 3954; 3958; 5801
+
CH2

Roberts, J.D.; Mazur, R.H. J. Am. Chem. Soc. 1951, 73, 3542
Brown, H.C. Science 1946, 103, 385
Brown, H.C.; Fletcher, R.S. J. Am. Chem. Soc. 1949, 71, 1845
Brown, H.C.; Berneis, H.L. J. Am. Chem. Soc. 1953, 75, 10
tBu

tBu

tBu
CH3

tBu

Cl

+
- Cl-

tBu

+

Bartlett, P.D. J. Chem. Educ. 1953, 30, 22

tBu

114
OTs

+
H+

- OTsHeck, R.; Prelog, V. Helv. Chim. Acta 1955, 38, 1541
Oxenium ions
R

O+

Reviews:
Dimroth, K. Top. Current Chem. 1985, 129, 99
AlCl3
OCl

+ AlCl3

O

O+

AlCl4 -

Cl

Martin, D.; Weise, A.; Becker, J. Chem. Ber. 1966, 99, 1266

O

.

R1

R3
O+
tBu
+

.
N

R3

R1

O
tBu
+

C
R4

R2

Rieker, A. Tetrahedron Lett. 1969, 2611

_
N

R3

tBu

R1

C

N

O

R3

N

R4

C
R4

R2

R1
R4

R2
R2

115
NO2

NO2

O2N

MeO

O
O

N+

NO2

Ph-OMe

OMe

- pyridine

+

+
O2N

BF4 -

OH

O

O+

Abramovitch, R.A.; Inbasekaran, M.; Kato, S. J. Am. Chem. Soc. 1973, 95, 5428
Abramovitch, R.A.; Alvernhe, G.; Inbasekaran, M.N. Tetrahedron Lett. 1977, 1113
Abramovitch, R.A.; Inbasekaran, M.N. Chem. Commun. 1978, 149
Abramovitch, R.A.; Alvernhe, G.; Bartnik, R.; Dassanayake, N.L.; Inbasekaran, M.N.; Kato, S. J. Am. Chem. Soc. 1981, 103, 4558
Abramovitch, R.A.; Bartnik, R.; Cooper, M.; Dassanayake, N.L.; Hwang, H.Y.; Inbasekaran, M.N.; Rusek, G. J. Org. Chem. 1982, 47, 4817
Abramovitch, R.A.; Bartnik, R.; Besse, J.; Kato, S. Nouveau J. Chim. 1984, 8, 571
Li, Y.; Abramovitch, R.A.; Houk, K.N. J. Org. Chem. 1989, 54, 2911

O

Ts

H+

NH

O+

O

OH

+

- TsNH 2
H

Endo, Y.; Shudo, K.; Okamoto, T. J. Am. Chem. Soc. 1977, 99, 7721
Shudo, K.; Orihara, Y.; Ohta, T.; Okamoto, T. J. Am. Chem. Soc. 1981, 103, 943
Endo, Y.; Shudo, K.; Okamoto, T. J. Am. Chem. Soc. 1982, 104, 6393
RO-

OH

RO+ + 2 e-

Bursey, M.M.; Hass, J.R.; Harvan, D.J.; Parker, C.E. J. Am. Chem. Soc. 1979, 101, 5489

Ph

Ph

116

O

HO

O

H+

- H+
O+

O

O

Deslongchamps, P.; Rowan, D.D.; Pothier, N. Heterocycles 1981, 15, 1093
Deslongchamps, P.; Rowan, D.D.; Pothier, N. Can. J. Chem. 1981, 59, 2787
O- AlCl3

O
Ph
N

O

AlCl3
N

O

+ Ph-O+

O

Uto, K.; Miyazawa, E.; Ito, K.; Sakamoto, T.; Kikugawa, Y. Heterocycles 1998, 48, 2593
OH
tBu

tBu

Br2
KBr

O

O

O
tBu

tBu

CH3 CN tBu
H2 O

tBu

tBu

tBu

+
tBu

R

tBu

Hegarty, A.F.; Keogh, J.P. J. Chem. Soc. Perkin Trans. 2 2001, 758

tBu

tBu

OH

117
O

O

O+

H2 O

OH
O

OH

Ph

- OAcPh

OAc

N3

N3 -

+

HO

Ph

N3

+

Ph
Ph

Novak, M.; Glover, S.A. J. Am. Chem. Soc. 2004, 126, 7748
Oxirene
O

R1

R2

Reviews:
Hopkinson, A.C.; Lien, M.; Yates, K.; Csizmadia, I.G. Prog. Theor. Org. Chem. 1977, 2, 230
Lewars, E.G. Chem. Rev. 1983, 83, 519
CrO3

O

Berthelot, M. Bull. Soc. Chim. Fr. 1870, 14, 113 (first claim; proven false)
Madelung, W.; Oberwegner, M.E. Naturwissenshaften 1929, 17, 430 (coining of acetylene oxide name)
Madelung, W.; Oberwegner, M.E. Ann. Chem. 1931, 490, 201 (second claim; proven false)

118
O

CH3 (CO)OOH
nBu

nBu
nBu

nBu

Schubach, H.; Franzen, V. Ann. Chem. 1952, 557, 60 (third claim; proven false)
O

O

hν or ∆

R1

R2
R1

- N2

R1

:

R2

O

R2

N2

McDonald, R.N.; Schwab, P.A. J. Am. Chem. Soc. 1964, 86, 4866
Stille, J.K.; Whitehurst, D.D. J. Am. Chem. Soc. 1964, 86, 4871
Barnes, M.F.; MacMillan, J. J. Chem. Soc. C 1967, 361
O

O

O



C*

C*

:

- N2

C*

N2


C*

C

O

C*

O

:

:

Me2 C* + CO + Me2 C

Csizmadia, I.G.; Font, J.; Strausz, O. J. Am. Chem. Soc. 1968, 90, 7360
Clark, D.T. Theor. Chim. Acta 1969, 15, 225
Thornton, D.E.; Gosavi, R.K.; Strausz, O. J. Am. Chem. Soc. 1970, 92, 1768

+ C*O

119
Dewar, M.J.S.; Trinajstic, N. Theor. Chim. Acta 1970, 17, 235
Rowland, F.S.; Russell, R.L. J. Am. Chem. Soc. 1970, 92, 7508

R2

*

- N2 R1

O

O
R2

*

R1

:

R1

O



*

R2

R1

*

R2

:

O

N2
R1
O

C

R1
O

*

C

*

R2

R2

ROH
O

R1

ROH
O

R1

*
*
RO

R2

RO

R2

Zeller, K.P.; Meier, H.; Kolshorn, H.; Mueller, E. Chem. Ber. 1972, 105, 1875
Meier, H.; Zeller, K.P. in Proc. 7th IUPAC Symp. Photochem., Katholieke U. Louvain: Louvain, Belgium, 1978, p. 234
Zeller, K.P. Chem. Ber. 1979, 112, 678
Zeller, K.P. Ann. Chem. 1979, 2036
Haiss, P.; Zeller, K.P. Z. Naturforsch. B 2003, 58, 595
Tanigaki, K.; Ebbesen, T.W. J. Am. Chem. Soc. 1987, 109, 5883 (proven to be false)
Tanaka, K.; Yoshimine, M. J. Am. Chem. Soc. 1980, 102, 7635 (ab initio calculations at 4-31G)

120

.

O

N

- HCN

- HCN

N

O

+

O

- CO2
O

O

O

Hop, C.E.C.A.; Holmes, J.L.; Terlouw, J.K. J. Am. Chem. Soc. 1989, 111, 441
Oxocarbons
_2

O

O

O

O

_2

O

_2

O

O

O
O

deltate

O

squarate

_2

O

O

O

O

O

O

O

croconate

O

rhodizonate

Reviews:
West, R. Aldrichimica Acta 1968, 1, 3
West, R.; Niu, J. in Chemistry of the Carbonyl Group, (J. Zabicky, ed.) Interscience: New York, 1970, Vol. 2, p. 241 - 275
West, R. Isr. J. Chem. 1980, 20, 300
West, R. (ed.) Oxocarbons, Academic Press: New York, 1980

121
O

O

HO

OH

HO

OH
O

KOMe
MeOH

O

_4
O

4 K+
O

O
O

West, R.; Niu, H.Y. J. Am. Chem. Soc. 1962, 84, 1324
CnOn-m
West, R.; Powell, D.L. J. Am. Chem. Soc. 1963, 85, 2577
Ito, M.; West, R. J. Am. Chem. Soc. 1963, 85, 2580 (squarate, croconate)
Patton, E.; West, R. J. Phys. Chem. 1970, 74, 2512 (rhodizonate)
West, R.; Eggerding, D.; Perkins, J.; Handy, D.; Tuazon, E.C. J. Am. Chem. Soc. 1979, 101, 1710 (deltate)
Oxonium ions
R1
O
R2

+
R3

Reviews:
Perst, H. Oxonium Ions in Organic Chemistry, Verlag Chemie: Weinheim, 1971
Perst, H. in Carbonium Ions, (G. Olah, P.v.R. Schleyer, eds.) Wiley: New York, 1976, Vol. 5, p. 1961
(i) Acetoxonium ions
Reviews:
None.

122

OTs

OH

H2 O
- OTs-

O

O

O

+

O

O

O

Winstein, S.; Hess, H.V.; Buckles, R.E. J. Am. Chem. Soc. 1942, 64, 2796
Winstein, S.; Buckles, R.E. J. Am. Chem. Soc. 1942, 64, 2780; 2787; 1943, 65, 613
(ii) Flavinium salts
Reviews:
None.
Blackburn, M.; Sankey, G.B.; Robertson, A.; Whalley, W.B. J. Chem. Soc. 1957, 1573
Dudley, K.H.; Ehrenberg, A.; Hemmerich, P.; Mueller, F. Helv. Chim. Acta 1964, 47, 1354
Dudley, K.H.; Hemmerich, P. Helv. Chim. Acta 1964, 47, 355
Walker, W.H.; Hemmerich, P.; Massey, V. Helv. Chim. Acta 1967, 50, 2269
(iii) Flavylium salts
Reviews:
Jurd, L. Recent Adv. Phytochem. 1972, 5, 135
Iacobucci, G.A.; Sweeny, J.G. Tetrahedron 1983, 39, 3005

123
R1
OH

R1

R2

H
H
pelargonin
H OH cyanidin
OH OH delphinidin
OMe OMe enidin (malvidin, syringidin)

+
HO

O
-

Cl

R2

Name

OH
OH

Pratt, D.D.; Robinson, R.; Williams, P.N. J. Chem. Soc. 1924, 125, 199
Robertson, A.; Robinson, R. J. Chem. Soc. 1926, 1713
Robertson, A.; Robinson, R. J. Chem. Soc. 1927, 242; 1710
Robertson, A.; Robinson, R. J. Chem. Soc. 1928, 1455; 1460
(iv) Meerwein salts
Reviews:
Kreher, R. Angew. Chem. Int. Ed. 1973, 12, 1022
Et
O
Et

Me

+

X-

O

Et

Me

+

XMe

X = BF 4 , SbCl 6 , AuCl4 , Bi 2 I7 , HgI3 , picrate,
1/2 SnCl6 , 1/2 PtCl6

Cl
O

3

Cl

O

+ 4 Et2 O...BF3 + 2 Et2 O

B

EtO

3

+ 3 Et3 O+ BF4 -

124

BF4 -

O+

Me2 O + BF3 + Et-F

Et

OO2N

NO2

Et3 O+

NO2

Meerwein, H.; Hinz, G.; Hofmann, P.; Kronig, E.; Pfeil, E. J. Prakt. Chem. 1937, 147, 257
RO

O

OMCl n-1

+ 2 R-O-R...MCln

+ R3 O+ MCln+1

Meerwein, H.; Battenberg, E.; Gold, H.; Pfeil, E.; Willfang, G. J. Prakt. Chem. 1939, 154, 83
Meerwein, H. Org. Synth. 1966, 46, 120
(v) Methoxonium ions
Reviews:
None.
OMe

OMe

Me
O+

- Br-

+

Br

Winstein, S.; Ingraham, L.L. J. Am. Chem. Soc. 1952, 74, 1160
(vi) Pyrylium salts

OH

H2 O

+
OMe

OMe

125
Reviews:
Balaban, A.T.; Schroth, W.; Fischer, G.W. Adv. Heterocyclic Chem. 1969, 10, 241
Balaban, A.T. Studies in Org. Chem. 1979, 3, 79
O

O



2

O

COOEt

O+

O

H3 O+

HX

X-

- CO2

O

OH

O

O

X = Cl, Br, I, PtCl6 , NO 3 , oxalate, tartrate, picrate, salicylate
Collie, J.N.; Tickle, T. J. Chem. Soc. Trans. 1899, 75, 710
Werner, A. Chem. Ber. 1901, 34, 3300
Decker, H.; von Fellen, T. Ann. Chem. 1907, 356, 281
Baeyer, A. Chem. Ber. 1910, 43, 2337
Willstätter, R. Sitzber. Preuss. Akad. Wissensch. 1914, 402
Willstätter, R.; Mallison, H. Sitzber. Preuss. Akad. Wissensch. 1914, 769
Dilthey, W. J. Prakt. Chem. 1916, 94, 53
Pfeiffer, P. Ann. Chem. 1917, 412, 253
Hanztsch, A. Chem. Ber. 1919, 52, 1535; 1544
Dilthey, W. J. Prakt. Chem. 1921, 102, 209
Gastaldi, C. Gazz. Chim. Ital. 1921, 5, 169
Dilthey, W. J. Prakt. Chem. 1922, 104, 28
R2
O

R2

HClO4 R1

O

R3

O

+
R1

R3

+ 2 R
4

O

R4

- H2 O
R4

Balaban, A.T.; Nenitzescu, C.D. Ann. Chem. 1959, 625, 74

O+

ClO4 -

R4

R4

OH

126
Balaban, A.T.; Nenitzescu, C.D. J. Chem. Soc. 1961, 3553; 3561; 3564
Praill, P.F.G.; Whitear, A.L. J. Chem. Soc. 1961, 3573
Praill, P.F.G.; Whitear, A.L. Proc. Chem. Soc. 1961, 312
Phenonium Ions
+

+

+
R1
R2

+

R4

R1

R4

R1

R4

R1

R4

R1

+
R3

R2

R3

R2

R3

R2

R3

R2

Reviews:
None.
Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3863
Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3871
Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3875
Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3883
Winstein, S.; Morse, B.K.; Grunwald, E.; Schreiber, K.C.; Corse, J. J. Am. Chem. Soc. 1952, 74, 1113
Winstein, S.; Brown, M.; Schreiber, K.C.; Schlesinger, A.H. J. Am. Chem. Soc. 1952, 74, 1140
Cram, D.J.; Elhafez, F.A.A.; Weingartner, H. J. Am. Chem. Soc. 1953, 75, 2293
Cram, D.J.; Elhafez, F.A.A. J. Am. Chem. Soc. 1953, 75, 3189
Laurent, A.; Mison, P. Bull. Soc. Chim. Fr. 1962, 956
Kresge, A.J.; Barry, G.W.; Charles, K.R.; Chiang, Y. J. Am. Chem. Soc. 1962, 84, 4343
Cram, D.J. J. Am. Chem. Soc. 1964, 86, 3767
Seidl, G.; Huisgen, R.; Wimmer, I. Ann. Chem. 1964, 677, 34
Olah, G.A.; Pittman, C.U. Jr. J. Am. Chem. Soc. 1965, 87, 3509
Olah, G.A.; Head, N.J.; Rasul, G.; Prakash, G.K.S. J. Am. Chem. Soc. 1995, 117, 875

R4
R3

127
Phenyl Cation (phenylium ion, arylium ion, benzene cation)
+
R

Reviews:
Ambroz, H.B.; Kemp, T.J. Chem. Soc. Rev. 1979, 8, 353

N2 + X
R

-

+
- N2

+ X-

X

R

R

Sandmeyer, T., Chem. Ber. 1884, 17, 1633
Sandmeyer, T., Chem. Ber. 1884, 17, 2650
Lewis, E.S. J. Am. Chem. Soc. 1958, 80, 1371
Kursanov, D.N.; Vol'pin, M.E.; Parnes, Z.N. Khim. Nauka i Prom. 1958, 3, 159
Franzen, V. Chem. Ztg. 1959, 83, 677
R

R

N2 +X

-

R

+

.
.

+ etc.

- N2
Taft, R.W. Jr. J. Am. Chem. Soc. 1961, 83, 3350
Hey, D.H.; Liang, K.S.Y.; Perkins, M.J. Tetrahedron Lett. 1967, 1477
Vul'fson, N.S.; Puchkov, V.A.; Nekrasov, Y.S. Izv. Akad. Nauk SSSR Ser. Khim. 1967, 1881
Friedman, L.; Chlebowski, J. J. Org. Chem. 1968, 33, 1633
Evleth, E.M.; Horowitz, P.M. J. Am. Chem. Soc. 1971, 93, 5636
Gleiter, R.; Hoffmann, R.; Stohrer, W.D. Chem. Ber. 1972, 105, 8
Kamigata, N.; Kobayashi, M.; Minato, H. Bull. Chem. Soc. Jpn. 1972, 45, 2047
Boettcher, H.; Becker, H.G.O.; Inanov, V.L.; Kusmin, M.G. Chimia 1973, 27, 437

128

+

+

N2

+ N2

Swain, C.G.; Sheats, J.E.; Harbison, K.G. J. Am. Chem. Soc. 1975, 97, 783
Swain, C.G.; Sheats, J.E.; Gorenstein, D.G.; Harbison, K.G. J. Am. Chem. Soc. 1975, 97, 791
Phosphenium ions
+
P
R2

R1

Reviews:
Cowley, A.H.; Kemp, R.A. Chem. Rev. 1985, 85, 367
Mazieres, M.R.; Roques, C.; Khim, T.; Majoral, J.P.; Wolf, R.; Sanchez, M. Phosphorus, Sulfur, and Silicon and the related elements 1990, 4950, 309
Burford, N.; Clyburne, J.A.C.; Losier, P.; Parks, T.M.; Cameron, T.S.; Richardson, J.F. Phosphorus, Sulfur, and Silicon and the related elements
1994, 53-54, 301
Guerret, O.; Bertrand, G. Acc. Chem. Res. 1997, 30, 486
Nakazawa, H. J. Organometallic Chem. 2000, 611, 349
Nakazawa, H. Adv. Organometallic Chem. 2004, 50, 108
R2 N

R2 N
P

Cl

LiAlH4

P+
-

"H "

R2 N

R

Cl

LiAlH4
P+

-

R

R

N
P

R = iPr, Et

H

R2 N

R

N

N

P

-

- Cl

R2 N

R2 N

- Cl

N
R

N
P

-

"H "

N
R

H

R = tBu

129

King, R.B.; Sundaram, P.M. J. Org. Chem. 1984, 49, 1784
Kibardin, A.M.; Litvinov, I.A.; Naumov, V.A.; Struchkov, Yu.T.; Gryaznova, T.V.; Mikhailov, Yu.B.; Pudovnik, A.N. Dokl. Akad. Nauk SSSR
1988, 298, 369
Wrackmeyer, B.; Schiller, J. Z. Naturforsch. 1992, 47B, 662
Kibardin, A.M.; Litvinov, I.A.; Naumov, V.A.; Struchkov, Yu.T.; Gryaznova, T.V.; Mikhailov, Yu.B.; Pudovnik, A.N. Dokl. Akad. Nauk SSSR
1994, 312, 623
tBu

tBu

N
P+

-

Cl

AgPF6

N
P+

N

PF 6 - + AgCl

N
tBu

tBu

tBu

tBu

N

Cl

AgPF6

N

P

P+

PF 6 - + AgCl

:
N

N
tBu

tBu

Denk, M.K.; Gupta, S.; Lough, A.J. Eur. J. Inorg. Chem. 1999, 41
Phosphonium ions
OR
RO

P+
R'

Reviews:

OR

130
Smith, D.J.H. Organophosphorus Chem. 1972, 4, 1
Smith, D.J.H. Organophosphorus Chem. 1973, 5, 1
Smith, D.J.H. Organophosphorus Chem. 1974, 6, 1
Smith, D.J.H. Organophosphorus Chem. 1976, 7, 1
Allen, D.W. Organophosphorus Chem. 1977, 8, 1
Allen, D.W. Organophosphorus Chem. 1978, 9, 1
Allen, D.W. Organophosphorus Chem. 1979, 10, 1
Smith, D.J.H. in Comprehensive Organic Chemistry, (I.O. Sutherland, ed.) Pergamon Press: Oxford, 1979, Vol. 2, p. 1127 - 1187
Allen, D.W. Organophosphorus Chem. 1980, 11, 1
Allen, D.W. Organophosphorus Chem. 1981, 12, 1
Allen, D.W. Organophosphorus Chem. 1983, 14, 1
Allen, D.W. Organophosphorus Chem. 1984, 15, 1
Allen, D.W. Organophosphorus Chem. 1985, 16, 1
Allen, D.W. Organophosphorus Chem. 1986, 17, 1
Allen, D.W. Organophosphorus Chem. 1987, 18, 1
Allen, D.W. Organophosphorus Chem. 1988, 19, 1
Allen, D.W. Organophosphorus Chem. 1989, 20, 1
Allen, D.W. Organophosphorus Chem. 1990, 21, 1
Allen, D.W. Organophosphorus Chem. 1991, 22, 1
Allen, D.W. Organophosphorus Chem. 1992, 23, 1
Allen, D.W. Organophosphorus Chem. 1993, 24, 1
Allen, D.W. Organophosphorus Chem. 1994, 25, 1
Cristan, H.J.; Plenat, F. in Chemistry of Organophosphorus Compounds, (F.R. Hartley, ed.) Wiley: Chichester, 1994, p. 45 - 183
Allen, D.W. Organophosphorus Chem. 1995, 26, 1
Allen, D.W. Organophosphorus Chem. 1996, 27, 1
Allen, D.W. Organophosphorus Chem. 1997, 28, 1
Allen, D.W. Organophosphorus Chem. 1999, 29, 1
Allen, D.W. Organophosphorus Chem. 2000, 30, 1
Stephan, D.W. Angew. Chem. Int. Ed. 2000, 39, 501
Allen, D.W. Organophosphorus Chem. 2001, 31, 1
Allen, D.W. Organophosphorus Chem. 2002, 32, 1
Allen, D.W. Organophosphorus Chem. 2003, 33, 1

131

CH3
CH3 O

P

OCH3

+ CH 3 I

CH3 O

P+

CH3
OCH3

I-

CH3 O

P

- CH3 I

OCH3

OCH3

Michaelis, A.; Kaehne, R. Chem. Ber. 1898, 31, 1048
Arbuzov, A.E. J. Russ. Phys. Chem. Soc. 1906, 38, 687
o-Quinodimethanes (o-Xylylenes)

.

CH2

.

CH2

Reviews:
Segura, J.L.; Martin, N. Chem. Rev. 1999, 99, 3199

.

CH2

.

CH2

Willstätter, R.; Veraguth, H. Chem. Ber. 1907, 40, 959
Bamberger, E.; Reber, E. Chem. Ber. 1907, 40, 2258
Fecht, H. Chem. Ber. 1907, 40, 3883
Ipatiev, V. Chem. Ber. 1908, 41, 993
Tshitshibabin, A.E. Chem. Ber. 1908, 41, 2770
Scholtz, M.; Wolfrum, R. Chem. Ber. 1910, 43, 2304
Chelintzev, V.V. Bull. Soc. Chim. Fr. 1936, 3, 1035
Esafov, V.I. J. Gen. Chem. USSR 1939, 9, 1841
Beilenson, B.; Hamer, F.M.; Rathbone, R.J. J. Chem. Soc. 1945, 222

OCH3

O

132
Lu're, S.I.; Shemyakin, M.M. J. Gen. Chem. USSR 1947, 17, 1356
Meyer, A.; Bouchet, G. Compt. Rend. 1948, 227, 345
Wittig, G.; Mangold, R.; Felletschin, G. Ann. Chem. 1948, 560, 116
Br
CHBr2

CHBr2

2 NaI
- 2 NaBr
- I2
Br

Br

.
.

Br

Br

Br

Cava, M.P.; Napier, D.R. J. Am. Chem. Soc. 1957, 79, 1701
p-Quinodimethanes (p-Xylylenes)

.

CH2

.

H2 C

Reviews:
None.
Schlenk, W.; Meyer, E. Chem. Ber. 1919, 52B, 8
pyrolysis
CH3

CH3

.

-2H

Szwarc, M. Nature 1947, 160, 403

p-xylene
CH2

CH2

n

133
Szwarc, M. Disc. Faraday Soc. 1947, 2, 46
Szwarc, M. J. Chem. Phys. 1951, 16, 319
Farmer, J.B.; Marsden, D.G.H.; Lossing, F.P. J. Chem. Phys. 1955, 23, 403
Errede, L.A.; Landrum, B.F. J. Am. Chem. Soc. 1957, 79, 4952
o-Quinonemethides and p-Quinonemethides
O

O

Reviews:
Fries, K.; Brandes, E. Ann. Chem. 1939, 542, 48
Wagner, H.U.; Gompper, R. in The Chemistry of Quinonoid Compounds, (S. Patai, ed.) Wiley: Chichester, 1974, p. 1145
Volod'kin, A.A.; Ershov, V.V. Usp. Khim. (Russ. Chem. Rev.) 1988, 57, 595
Wagner, H.U.; Gompper, R. in The Chemistry of Quinonoid Compounds, (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1988. Vol. 2.
Amouri, H.; Le Bras, J. Acc. Chem. Res. 2002, 35, 501
Staudinger, H.; Bereza, S. Ann. Chem. 1911, 380, 243
Gomberg, M. J. Am. Chem. Soc. 1913, 35, 1035
Schlenk, W.; Brauns, M. Chem. Ber. 1914, 46, 4061
Pummerer, R.; Melamed, D.; Puttfarcken, H. Chem. Ber. 1922, 55B, 3116
Lindemann, H. Ann. Chem. 1923, 431, 270
Lindemann, H.; Forth, H. Ann. Chem. 1923, 435, 219
Shoruigin, P. Chem. Ber. 1927, 60B, 2373
Goldschmidt, S.; Sadler, A.; Gelber, E.; Schlosser, H.; Vogt, A. Chem. Ber. 1928, 61B, 829
Shorigin, P. Chem. Ber. 1928, 61B, 2516

134
Ar
O

2 nBuLi
HO

I

Ar

Ar
Li+ -O

O

Li

- nBuI
- nBuOH

Ar

Hünig, S.; Schweeberg, H.; Schwarz, H. Ann. Chem. 1954, 587, 132
Hünig, S.; Schwarz, H. Ann. Chem. 1956, 599, 131
X

X

FVT

X = O, S, NH
Pfister-Guillouzo, G.; Gracian, F.; Senio, A.; Letulle, M.; Ripoll, J.L. Tetrahedron Lett. 1992, 33, 5753
R1

R1

R2
OH



R2

- H2 O
HO

O

Wan, P.; Barker, B.; Diao, L.; Fischer, M.; Shi, Y.; Yang, C. Can. J. Chem. 1996, 74, 465
Chiang, Y.; Kresge, A.J.; Zhu, Y. J. Am. Chem. Soc. 2000, 122, 9854
Chiang, Y.; Kresge, A.J.; Zhu, Y. J. Am. Chem. Soc. 2002, 124, 6349
Chiang, Y.; Kresge, A.J.; Zhu, Y. Photochem. Photobiol. Sci. 2002, 1, 67

135

Chang, J.A.; Kresge, A.J.; Zhan, H.Q.; Zhu, Y. J. Phys. Org. Chem. 2004, 17, 579

O

O

Cevasco, G.; Pardini, R.; Thea, S. Eur. J. Org. Chem. 1998, 665
Radicals
Reviews:
Gomberg, M. Chem. Rev. 1925, 1, 91
Trans. Faraday Soc. 1934, 30, 1 - 246 (symposium on radicals)
Hey, D.H.; Waters, W.A. Chem. Rev. 1937, 21, 169
Steacie, E.W.R. Free Radical Mechanisms, Reinhold Publishing Corp.: New York, 1946
Steacie, E.W.R. Atomic and Free Radical Reactions, 2nd ed., Reinhold Publishing Corp.: New York, 1954
Lossing, F.P. Ann. N.Y. Acad. Sci. 1957, 67, 499
Waters, W.A. (ed.) Vistas in Free-Radical Chemistry, Pergamon Press: New York, 1959
Symons, M.C.R. Adv. Phys. Org. Chem. 1963, 1, 284
Friedlina, R.K. Adv. Free Radical Chem. 1965, 1, 211
Norman, R.O.C. Adv. Phys. Org. Chem. 1967, 5, 53
Forrester, A.R.; Hay, J.M.; Thomson, R.H. Organic Chemistry of Stable Free Radicals, Academic Press: New York, 1968
Janzen, E.G. Acc. Chem. Res. 1969, 2, 279
Bennett, J.E.; Mile, B.; Thomas, A.; Ward, B. Adv. Phys. Org. Chem. 1970, 8, 1
Kochi, J.K. (ed.) Free Radicals, Wiley: New York, Vol. 1 - 2, 1973
Huyser, E.S. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 1
Zahradnik, R.; Carsky, P. Prog. Phys. Org. Chem. 1973, 10, 327
Neta, P. Adv. Phys. Org. Chem. 1976, 12, 224
Griller, D.; Ingold, K.U. Acc. Chem. Res. 1976, 9, 13
Griller, D.; Ingold, K.U. Acc. Chem. Res. 1980, 13, 193
Ballester, M. Acc. Chem. Res. 1985, 18, 380 (inert free radicals)

136
Russell, G.A. Adv. Phys. Org. Chem. 1987, 23, 271
Ballester, M. Adv. Phys. Org. Chem. 1989, 25, 307; 321 (inert free radicals)
Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Organic Chemistry, Wiley: New York, 1995
Arnold, B.R.; Bucher, G.; Netto-Ferreira, J.C.; Platz, M.S.; Scaiano, J.C. Biradicals, Radicals in Excited States, Carbenes, and Related Species,
Springer-Verlag: Weinheim, 1998
Saveant, J.M. Adv. Phys. Org. Chem. 2000, 35, 117
Rathore, R.; Kochi, J.K. Adv. Phys. Org. Chem. 2000, 35, 193
Tidwell, T.T. Adv. Phys. Org. Chem. 2001, 36, 1
Zipse, H. Adv. Phys. Org. Chem. 2003, 38, 111
Power, P.P. Chem. Rev. 2003, 103, 789 (stable radicals of heavier main group elements)
Hicks, R.G. Can. J. Chem. 2004, 82, 1119 (stable radicals)
stabilities of free radicals:
Bowden, S.T.; Jones, W.J. J. Chem. Soc. 1928, 1149 (from dimer dissociation equilibria)
Bent, H.E.; Cline, J.E. J. Am. Chem. Soc. 1936, 58, 1624 (from thermochemical techniques)
Cohen, S.G.; Cohen, F.; Wang, C.H. J. Org. Chem. 1953, 28, 1749 (from kinetic techniques)
Henglein, A. Electroanal. Chem. 1976, 9, 163 (from pulse radiolysis polarography)
Carbon centred radicals
(i) Gomberg radical
Ph

Ph

Zn

Cl
Ph

Ph

Ph

.

+ Cl

.

Ph
Ph

Ph

2
Ph

.

Ph

Ph
Ph
Ph

Ph

Gomberg, M., J. Am. Chem. Soc. 1900, 22, 757

H

137
Gomberg, M. Chem. Ber. 1900, 33, 3150
Gomberg, M. Chem. Ber. 1901, 34, 2726
Gomberg, M.; Bachmann, W.E. J. Am. Chem. Soc. 1924, 46, 2339
Lankamp, H.; Nauta, W.T.; MacLean, C. Tetrahedron Lett. 1968, 249 (correct structure of radical dimer product)

.

2 Ph3 C

+ O2

Ph3 C-O-O-CPh3

Gomberg, M.; Cone, L.H. Chem. Ber. 1904, 37, 3538
Schmidlin, J. Chem. Ber. 1908, 41, 2471
(ii) Alkyl radicals
Reviews:
Steacie, E.W.R. Atomic and Free Radical Reactions, 2nd ed., Reinhold: New York, 1954
Norrish, R.G.W.; Thrush, B.A. Quart. Rev. Chem. Soc. 1956, 10, 149
Davidson, N. J. Chem. Educ. 1957, 34, 126
Ramsay, D.A. Ann. N.Y. Acad. Sci. 1957, 67, 485
Lossing, F.P. Ann. N.Y. Acad. Sci. 1957, 67, 499
Kutschke, K.O.; Steacie, E.W.R. in Vistas in Free Radical Chemistry, (W.A. Waters, ed.) Pergamon Press: New York, 1959, p. 162
O


R

O

Cl

RCl +

Chattaway, F.D.; Backeberg, O.G. J. Chem. Soc. 1923, 123, 2999
Ph-R + PhCOOH + CO2
(PhCOO)2 + R-H
Ph-H + PhCOOR + CO2

138
Gelissen, H.; Hermans, P.H. Chem. Ber. 1925, 58, 984



. .

R

R4 Pb

+

PbR 3

Paneth, F.; Hofeditz, W. Chem. Ber. 1929, 62, 1335 (gas phase)
Paneth, F.; Lautsch, W. Chem. Ber. 1931, 64, 2702
Paneth, F.; Herzfeld, K. Z. Elektrochem. 1931, 37, 577
Paneth, F. Trans. Faraday Soc. 1934, 30, 179
CH3 Cl, CH 2 Cl2 , CHCl 3 , CCl 4

CH4 + Cl2

Pease, R.N.; Walz, F. J. Am. Chem. Soc. 1931, 53, 3728
O

Cl2 C=CCl2 + 1/2 O2
Cl3 C

Cl

Dickinson, R.A.; Leermakers, P.A. J. Am. Chem. Soc. 1932, 54, 3852
Br
Br

Br

HBr
Br

HBr

Br

(absence of O2 )
Br

O2
Kharasch, M.S.; Mayo, F.R. J. Am. Chem. Soc. 1933, 55, 2468 (peroxide effect)
Kharasch, M.S.; Engelmann, H.; Mayo, F.R. J. Org. Chem. 1937, 2, 288
Kharasch, M.S.; Mayo, F.R. J. Am. Chem. Soc. 1938, 60, 3097

139
chlorination of aliphatic hydrocarbons:
Hass, H.B.; McBee, E.T.; Weber, P. Ind. Eng. Chem. 1935, 27, 1190
Hass, H.B.; McBee, E.T.; Weber, P. Ind. Eng. Chem. 1936, 28, 333
Vaughan, W.E.; Rust, F.F. J. Org. Chem. 1940, 6, 449
Rust, F.F.; Vaughan, W.E. J. Org. Chem. 1941, 7, 479
Kharasch, M.S.; Mansfield, J.V.; Mayo, F.R. J. Am. Chem. Soc. 1937, 59, 1155

CH2

C

n
COOMe

COOMe

Melville, H.W. Proc. Roy. Soc. London 1937, 163A, 511
O
O
Ph

Ph

O
O

Brodie, B.C. Ann. Chem. 1858, 108, 79
O
O
Ph
R

H

Ph

O
O

+ SO2 Cl2

R

Cl

+ SO2 + HCl + 2 CO2 + 2 PhCl

Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1939, 61, 2142; 3432
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 925

R

H

+ SO2 + Cl2

R

SO2 Cl

+ HCl

140

Reed, C.F. US 2,174,494 (1939)
Kharasch, M.S.; Chao, T.H.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 2393
O

O


R

H

+

+ HCl

Cl

Cl

Cl

R

O
R

H

O
Cl

+


+ HCl + CO

Cl

Cl

R
O

Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 454
OH

HBr
2

Zn
2

Ph

.

Br

- H2 O

2

Ph

ZnBr2

Ph

Ph

Ziegler, K.; Deparade, W. Ann. Chem. 1950, 567, 123
Cl
Cl

4 CH2 =N 2 + CCl4

4 N2 +
Cl
Cl

Urry, W.H.; Eiszner, J.R. J. Am. Chem. Soc. 1952, 75, 5822

Ph

141

NC

N

N

CN

+ O2

OOH

(AIBN)
Jones, G.G. US 2,681,936 (1954)
detection of free radicals in solution:
Kharasch, M.S.; Mulley, R.D.; Nudenberg, W. J. Org. Chem. 1954, 19, 1477
Kharasch, M.S.; Holton, P.G.; Nudenberg, W. J. Org. Chem. 1954, 19, 1600
Kharasch, M.S.; Nudenberg, W. J. Org. Chem. 1954, 19, 1921
Kharasch, M.S.; Holton, P.G.; Nudenberg, W. J. Org. Chem. 1955, 20, 920
Herzberg, G.; Shoosmith, J. Can. J. Phys. 1956, 34, 523 (detection of methyl radical)
O

O

H2 O2
Ph
Ph

O

OEt

Huyser, E.S.; Garcia, Z. J. Org. Chem. 1962, 27, 2716
CX4 + CH 2 =CHR

X3 C-CH2 -CHXR

X = Cl, Br

Walling, C.; Huyser, E.S. Org. React. 1963, 13, 122

Ph

N

N

2

Ph

- N2

Ph

.

Nelsen, S.F.; Bartlett, P.D. J. Am. Chem. Soc. 1966, 88, 137
Nelsen, S.F.; Bartlett, P.D. J. Am. Chem. Soc. 1966, 88, 143

142

tBu-O-O-tBu
CH3

2 tBu-O
+ tBuO

.

.

tBuOH +

CH2

.

Kochi, J.K.; Krusic, P.J.; Eaton, D.R. J. Am. Chem. Soc. 1969, 91, 1877
Kochi, J.K.; Krusic, P.J.; Eaton, D.R. J. Am. Chem. Soc. 1969, 91, 1879
tBu-O-O-tBu
N

CH3

2 tBu-O
+ tBuO

.

.

tBuOH +

N

CH2

.

Danen, W.C.; West, C.T.; Kensler, T.T. J. Am. Chem. Soc. 1973, 95, 5716
Danen, W.C.; West, C.T. J. Am. Chem. Soc. 1974, 96, 2447
(iii) Aryl radical (phenyl radical)
Reviews:
Taylor, G.W. Can. J. Chem. 1957, 35, 739
Williams, G.H. Homolytic Aromatic Substitution, Pergamon Press: London, 1960
Porter, G.G. in Molecular Spectroscopy (P. Hepple, ed.) Proc. Conf. 4th, 1968, 305
Bolton, R.; Williams, G.H. Chem. Soc. Rev. 1986, 15, 261
Galli, C. Chem. Rev. 1988, 88, 765
Brown, R.F.C. Eur. J. Org. Chem. 1999, 3211

.
R

143
O
Ph

Ph

N

N

N

Ph

O
O

NO

- N2

. .
+

Ph-H
OAc

Ph-Ph + HOAc

Bamberger, E. Chem. Ber. 1895, 28, 403
Bamberger, E. Chem. Ber. 1897, 30, 366
Waters, W.A. J. Chem. Soc. 1937, 113
O
O2N

N

N

O - Na+

+

R

Cl

O2N

N

N

O

- NaCl

O
R

O2N

N

N

O

O2N
O

R

Kühling, O. Chem. Ber. 1895, 28, 41
Kühling, O. Chem. Ber. 1896, 29, 165

- N2

. .

O

Ph-H

+

O

+

O2N
O

R

Ph

HO

R

144

. .
+ X

X
R1

R1

.

2
R1

R1

Cu+2 + 2 e-

Cu

.

R1

2 X + 2 e-

2 X-

Ullmann, F. Ann. Chem. 1904, 332, 38 (Ullmann coupling reaction)
Rapson, W.S.; Shuttleworth, R.G. Nature 1941, 147, 675
NaOH
Ar1

N2 +

X

-

+

Ar2

H

Ar1

Ar2

+ N 2 + HX

Gomberg, M.; Bachmann, W.E. J. Am. Chem. Soc. 1924, 46, 2339
Gomberg, M.; Pernert, J.C. J. Am. Chem. Soc. 1926, 48, 1372
Levy, J. Bull. Soc. Chim. Fr. 1923, 33, 1655
Reihlen, H.; Illig, R.; Wittig, R. Chem. Ber. 1925, 58B, 12
Levy, J. Bull. Soc. Chim. Fr. 1926, 39, 67
Tiffeneau, M.; Levy, J. Bull. Soc. Chim. Fr. 1931, 49, 1806
Bates, J.R.; Taylor, H.S. J. Am. Chem. Soc. 1927, 49, 2438 (first free radical chain mechanism for gas phase polymerization of ethylene)
PbPh 4
Ph

. .
.

2 Ph

+

Ph

+

Hg

4 Ph

.

+

Pb
Ph-Ph
Ph2 Hg

145
Dull, M.F.; Simons, J.H. J. Am. Chem. Soc. 1933, 55, 3898
Ph

Ph

+ Na (g)

Br

.

+ NaBr

Horn, E.; Polanyi, M. Z. Physik. Chem. 1934, 25B, 151
Ph

N

N

CPh3

+ Ph-H

Ph
- N2

.

+ Ph 3 C

.

Ph-H
Ph-Ph + Ph3 CH

O
O
O
Ph

Ph

2

O

Ph
O
Ph

N

N

Ph

OAc

- N2
PhCH 2

N

N

OAc

- N2

..
+

O

.

Ph
- CO2

.

+ PhCOO

.

OAc

PhCH 2

..
+

OAc

NO
N

+ Ph-H

Ph

Ph-Ph + N2 + CH 3 COOH

O
NO
N

+ Ph-H

PhCH 2

PhCH 2 Ph + N 2 + CH 3 COOH

O

Grieve, W.S.M.; Hey, D.H. J. Chem. Soc. 1934, 1797 (homolytic aromatic substitution)
Hey, D.H. J. Chem. Soc. 1934, 1966

Ph-H
Ph-Ph + PhCOOH

146

150 C
Ph

Ph2 Hg + Ph-NH-NH-Ph
150 C
Ph4 Pb + S
150 C
Ph4 Sn + S

Ph
Ph

.
.

.

2 Ph-H + Hg + Ph-N=N-Ph

Ph-S-S-Ph + PbS
Ph-S-S-Ph + SnS2

Razuvaev, G.A.; Koton, M.M. Zh. Obshchei Khim. 1935, 5, 361
Koton, M.M. Zh. Obshchei Khim. 1932, 2, 345
O
O
Ph
R

H

Ph

O
O

+ SO2 Cl2

R

Cl

+ SO2 + HCl + 2 CO2 + 2 PhCl

Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1939, 61, 2142; 3432
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 925
N2 + Cl-

+

Ph

- N2
- HCl

N

N

Haworth, J.W.; Heilbron, I.M.; Hey, D.H. J. Chem. Soc. 1940, 349
Hey, D.H.; Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1955, 3963
Ar

N

N

NMe2

Ar
- N2

.

+

Elks, J.; Hey, D.H. J. Chem. Soc. 1943, 441

Me2 N

.

R-H
Ar-R + Me2 NH

147
Hardie, R.L.; Thomson, R.H. J. Chem. Soc. 1958, 1286
Basterfield, S.; Dyck, A.J. Can. J. Res. 1942, 20B, 240
Tiffeneau, M.; Tchoubar, B.; Le Tellier, S. Compt. Rend. 1943, 217, 588
Huisgen, R.; Horeld, G. Ann. Chem. 1949, 562, 137
Szwarc, M.; Williams, D. J. Chem. Phys. 1952, 20, 1171
Jacquiss, M.T.; Szwarc, M. Nature 1952, 170, 312
Ingold, K.U.; Lossing, F.P. Can. J. Chem. 1953, 31, 30
[PhCOO]4 Pb
Ph

.

+

4 Ph

.

+

4 CO2

Ph-Ar +

Ar-H

+
H

.

Pb

Hey, D.H. Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1954, 2747
Ph

Ph

NHPh

LiAlH4

N

NH

H2 O2

N
Ph

Ph

Ph

decalin
Ph-H + Ph2 CH-CHPh 2

NPh

Ph

major
N
Ph

Ph2 CH2

NPh

Ph

NHPh

Ph-H + Ph2 CH-CHPh 2
major

148
Cohen, S.G.; Wang, C.H. J. Am. Chem. Soc. 1955, 77, 3628
Ph4 Pb + AgNO3

Ph

.

2 Ph

Ph

.

+ Ag + Ph 3 PbNO3
OH

+

EtOH

.

Ph-H +

.

H

Ph-Ph

Spice, J.E.; Twist, W. J. Chem. Soc. 1956, 3319
O(CO)Ph
Ph

O

I

- PhI

Ph

O

O(CO)Ph

.

Ar-H

.

PhCOOAr + H

- CO2

Ph

.

Ar-H
Ph-Ar

+

H

.

Hey, D.H.; Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1956, 1475
Ag2 O
PhNHNH2

Ph

- H2 O
- 2 Ag

N

N

H

Ph
- N2

. .
H

Ph-H

Ar-H

Ph-Ph
Hardie, R.L.; Thomson, R.H. J. Chem. Soc. 1957, 2512

+

Ph-Ar + H

.

149
O

H
Ph

N

N

C

+

Ph

Ph

N

N

. .
+

O
C

CH3 OH
Ph

N

NH

+ CH3 O

Ph

O
C

Ph

- N2

Ph-H

Ph

. .
+ H

Cohen, S.G.; Nicholson, J. J. Am. Chem. Soc. 1964, 86, 3892
Cohen, S.G.; Nicholson, J. J. Org. Chem. 1965, 30, 1162
Porter, G.; Ward, B. Proc. Roy. Soc. London A 1965, 287, 457 (UV spectrum in gas phase)
Cercek, B.; Kongshaug, M. J. Phys. Chem. 1970, 74, 4319 (UV spectrum in aqueous solution)
Ikeda, N.; Nakashima, N.; Yoshihara, K. J. Am. Chem. Soc. 1985, 97, 3381 (UV spectrum in gas phase)
OH
tBu

OH
tBu



tBu

tBu

+ Br

Br

.

.

150
OH

OH
tBu tBu

tBu

O

OH
tBu

tBu

.

tBu tBu

tBu

+

+

.
Br

Br

Lappin, G.R.; Zannucci, J.S. Tetrahedron Lett. 1969, 5085
308 nm
Ph

Ph-N=O
Ar 12 K

..
+

N=O

Engbert, J.M.; Dick, B. Appl. Phys. B 1996, 63, 531
Engbert, J.M.; Slenczka, A.; Kensy, U.; Dick, B. J. Phys. Chem. 1996, 100, 11883
(iv) Benzoyl radical
O

.
Reviews (acyl or acetyl radicals):
Vinogradov, M.G.; Nikishin, G.I. Usp. Khim. 1971, 40, 1960
Caronna, T.; Minisci, F. Rev. Reactive Species in Chemical Reactions 1976, 1, 263
Boger, D.L. Isr. J. Chem. 1997, 37, 9349
Chatgilialoglu, C.; Crich, D.; Komatsu, M.; Ryu, I. Chem. Rev. 1999, 99, 1991

151
O

O

2

+ Zn
Ph

2

Cl
O

2

.

.

+ ZnCl2

Ph
O

O

+ 1/2 O2

Ph

Ph

O

Ph

Norris, J.F.; Franklin, D.R. Am. Chem. J. 1903, 29, 141 (suggestion)
O

O

.


Ph

Ph

Ph

.

Ph

2 Ph

.

O

O

2

+ Ph

Ph
Ph

.

O

Ph-Ph

Glazebrook, H.H.; Pearson, T.G. J. Chem. Soc. 1939, 589
O

Ph

.

.

Ph
N

+
Ph

N

N

Ph
N

Ph

O
Ph

152
Kharasch, M.S.; Zimmerman, M.; Zimmt, W.; Nudenberg, W. J. Org. Chem. 1953, 18, 1045

.

Ph

+ Ph-CHO
Ph

O

O

.

Ph

.

O

O

+

.

N

Ph

O
N
Ph

Kharasch, M.S.; Schwartz, D.; Zimmerman, M.; Nudenberg, W. J. Org. Chem. 1953, 18, 1051
O
N
Ph

O

Ph ∆
- N2

N

2
Ph

.

O

Mackay, D.; Marx, U.F.; Waters, W.A. J. Chem. Soc. 1964, 4793
O

O


Br

- Br

.

.

R

R

R = H, Cl, OMe
Schmidt, U.; Kabitzke, K.H.; Markau, K. Angew. Chem. 1965, 77, 378
Schmidt, U.; Kabitzke, K.H.; Markau, K. Monatsh. Chem. 1966, 97, 1000

153
O
tBuO

O
O

2 CO2 + 2 tBuO

OtBu
O

.
.

tBuO

+

.

.

tBuOH + Ph-C=O

Ph-CHO

O

Ph-C=O + R-N=O

Ph

N
O

.

R

Mackor, A.; Wajer, T.A.J.W.; de Boer, T.J. Tetrahedron 1968, 24, 1623
Krusic, P.J.; Rettig, T.A. J. Am. Chem. Soc. 1970, 92, 724 (ESR)
I2
Ph-CHO + I

.

2I

.

..

Ph-C=O + HI
Ph

Ph-C=O + I2

C

+ I

O

.

I

Solly, R.K.; Benson, S.W. J. Am. Chem. Soc. 1971, 93, 1592
O

O
Ph

Ph



+

Ph
OR

. .
OR

Ph

154
O

Ph

O

O

.

+

.

N

N

Ph

Ph

tBu

O

Ledwith, A.; Russell, P.J.; Sutcliffe, L.H. J. Chem. Soc. Perkin Trans. 2 1972, 1925
Simoes, J.A.M.; Griller, D. Chem. Phys. Lett. 1989, 158, 175 (photoacoustic calorimetry of benzoyl radical)
(v) Acyl radical
O

.

R

Reviews:
Vinogradov, M.G.; Nikishin, G.I. Usp. Khim. 1971, 40, 1960
Caronna, T.; Minisci, F. Rev. Reactive Species in Chemical Reactions 1976, 1, 263
Chatgilialoglu, C.; Crich, D.; Komatsu, M.; Ryu, I. Chem. Rev. 1999, 99, 1991

(COCl)2
1o

2


(COCl)2

.

.

COCl

COCOCl + Cl

.

155

.
.

COCl

CO + Cl

COCOCl
RH + Cl

2o

.
.

R

.

2 CO + Cl

.

R

+ (COCl)2

COCl

.

.

+ HCl

RCOCl +
CO + Cl

.

.

COCl

Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1942, 64, 329
Kharasch, M.S.; Kane, S.S.; Brown, H.C. J. Am. Chem. Soc. 1942, 64, 1621


.
.

(CH3 )2 C=O
CH3 -C=O

CH3 + CH 3 -C=O

CO +

CH3 -C=O + O2

.

CH3

.

.

.

CH3

. .?
.
.

CH3 COO + O

CH3

CH4 +

+ (CH 3 )2 C=O

O

CH2

CH3

.
.

O

CH2

CH3

+ O2

+ O2

CH3 COOH + H-C=O

.

H-C=O

+ H2O

156

.
.
.

H-C=O
H-C=O
H

CO + H

.

CO2 + OH

+ O2

.

+ O2

.

HOO

Marcotte, F.B.; Noyes, W.A. Jr. J. Am. Chem. Soc. 1952, 74, 783
tBu-O-O-tBu

.
.
.

.

tBuO
CH3

tBuO

2 tBuO

CH3 +

(CH 3 )2 C=O

..

+ CO

.

CH3 -C=O

+ CO

tBu

+

CO2

Porter, G.B.; Benson, S.W. J. Am. Chem. Soc. 1953, 75, 2773
O

O

O
N

.

2

N

- N2

Cramer, R. J. Am. Chem. Soc. 1957, 79, 6215
RCHO
-H

.

.

RCO
k2

k1

CO + R

CCl4

RCOCl +

H

.

CCl3

.

. .
Cl

RH

RCl

157
Applequist, D.E.; Kaplan, L. J. Am. Chem. Soc. 1965, 87, 2194
nBu3 Sn-H

nBu3 Sn

O

+ nBu3 Sn
R

. .
+

O

.

X
O

H

.

+ nBu3 Sn-X

R
O

. .
+ H

R

R
O

R

R

.

.

.

+
O

R

H

+ CO

nBu3 Sn-H

R-H + nBu 3 Sn

.

O

. .
+ R

R

R

R

R = PhCH 2, Ph3C, PhCH2O
Kuivila, H.G.; Walsh, E.J. Jr. J. Am. Chem. Soc. 1966, 88, 571
Walsh, E.J. Jr.; Kuivila, H.G. J. Am. Chem. Soc. 1966, 88, 576

158
O

O

Ph



Ph

Ph

.
.
.

CO + Ph-CH 2

.

Ph-CH 2 + Ph-CH 2
Ph-CH 2

+ O2

Ph-CH 2 O-O

+ Ph-CH 2

.

O
Ph

. .

. .

PhCH 2 CH2 Ph
Ph-CH 2 O-O

+ Ph-CH 2

.

Ph-CH 2 -O-O-CH2 -Ph

Maillard, B.; Ingold, K.U.; Scaiano, J.C. J. Am. Chem. Soc. 1983, 105, 5095
Lunazzi, L.; Ingold, K.U.; Scaiano, J.C. J. Phys. Chem. 1983, 87, 529
(vi) Benzyl radical

.

CH2

Reviews:
Porter, G. Chem. Soc. Special Publ. 1957, 9, 139
Lei, X. Res. Chem. Intermediates 1990, 14, 15
3 PhCH 3 Cl + AsCl3 + 6 Na
(PhCH 2 )3 As + 3 PhCH 2 Cl

(PhCH 2 )3 As + 6 NaCl
(PhCH 2 )2 AsCl3 + 2 PhCH 2 CH2 Ph

159

Michaelis, A.; Paetow, U. Ann. Chem. 1886, 233, 60
Dodonov, J.; Medox, H. Chem. Ber. 1935, 68B, 1254
CH3


Br2

CH2 Br

Kharasch, M.S.; Margolis, E.; White, P.C.; Mayo, F.R. J. Am. Chem. Soc. 1937, 59, 1405
Kharasch, M.S.; White, P.C.; Mayo, F.R. J. Org. Chem. 1938, 3, 3
Blades, A.T.; Steacie, E.W.R. Can. J. Chem. 1954, 32, 1142 (pyrolysis of toluene)
Norman, I.; Porter, G. Proc. Roy. Soc. London 1955, 230A, 399
Porter, G.; Wright, F. Trans. Faraday Soc. 1955, 51, 1469
Beckwith, A.L.J.; Waters, W.A. J. Chem. Soc. 1957, 1001 (benzyl radicals reacting with anthracene)
Porter, G.; Windsor, M.W. Nature 1957, 180, 187
Porter, G.; Strachan, E. Trans. Faraday Soc. 1958, 54, 1595
Porter, G.; Strachan, E. Spectrochim. Acta 1958, 12, 299
PhCH 2 -Cl
2 PhCH 2 + + Fe

.

2 PhCH 2

PhCH 2 + + Cl2 PhCH 2

.

+ Fe+2

PhCH 2 -CH2 Ph

Sisido, K.; Udo, Y.; Nozaki, H. J. Am. Chem. Soc. 1960, 82, 434
Hodgkins, J.E.; Megarity, E.D. J. Am. Chem. Soc. 1965, 87, 5322 (EPA solid matrix)

160
tBuOOtBu

2 tBuO

CH3

+ tBuO

.

.

.

CH2

+ tBuOH

R

R

Kennedy, B.R.; Ingold, K.U. Can. J. Chem. 1966, 44, 2381
(vii) Koelsch radical
Ph

.

Koelsch, C.F. J. Am. Chem. Soc. 1932, 54, 4744
Koelsch, C.F. J. Am. Chem. Soc. 1957, 79, 4439
Group IV centred radicals except carbon (Si, Ge, Sn)
(i) Silyl
R1

.
Si

R3

R2

Reviews:
Jackson, R.A. Adv. Free Radical Chem. 1969, 3, 231

161
Jackson, R.A. Chem. Soc. Special Publ. 1970, 295
Sakurai, H. in Free Radicals, (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 741
Arthur, N.L.; Bell, T.N. Rev. Chem. Intermediates 1978, 1, 37
Alberti, A.; Pedulli, G.F. Rev. Chem. Intermediates 1987, 8, 207
Dohmaru, T. in Reactions of Special Radicals in Chemical Kinetics of Small Organic Radicals, (Z.B. Alfassi, ed.) CRC Press: Boca Raton, 1988,
Vol. 3, p. 165
Chatgilialoglu, C. NATO ASI Ser. Ser. C. 1989, 257, 119
Chatgilialoglu, C. NATO ASI Ser. Ser. C. 1989, 260, 115
Chatgilialoglu, C. Chem. Rev. 1995, 95, 1229
Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1
Chatgilialoglu, C.; Schiesser, C.H. in The Chemistry of Organic Silicon Compounds, (Z. Rappoport, S. Patai, eds.) Wiley: Chichester, 2001, Vol. 3,
p. 341

H3 Si

2 H3 Si

SiH3

.


H3 Si

SiH2

H3 Si

SiH2

.

H3 Si

SiH3

H3 Si

.

.

+

H3 Si

SiH2

.

:

+ H 2 Si

Emeleus, H.J.; Reid, C. J. Chem. Soc. 1939, 1021 (pyrolysis of disilane and trisilane)
(CH3 COO)2
Cl3 SiH +
(CH3 COO)2
CH3 COO

.

CH3

+ HSiCl3

5

5

.



2 CH3 COO

.

CH3

+ CO2

Cl3 Si

.

CH4 + Cl3 Si

162

R-CH=CH 2 + Cl3 Si

.

R-CH-CH 2 SiCl3

.

.

R-CH-CH 2 SiCl3

.

R-CH2 -CH2 SiCl3 + Cl3 Si

+ HSiCl3

Sommer, L.H.; Pietrusza, E.W.; Whitmore, F.C. J. Am. Chem. Soc. 1947, 69, 188 (first suggestion)
Burkhard, C.A.; Krieble, R.H. J. Am. Chem. Soc. 1947, 69, 2687
Barry, A.J.; DePree, L.; Gilkey, J.W.; Hook, D.E. J. Am. Chem. Soc. 1947, 69, 2916
SiCl3

(PhCOO)2
HC

+ Cl3 SiH

CH

(PhCOO)2
RCH

CH2

via Cl3 Si

SiCl3

+ Cl3 SiH

.

RCH 2

Burkhard, C.A.; Krieble, R.H. J. Am. Chem. Soc. 1947, 69, 2687

F

F

Me2 SiH2 +

Me



Me

CF2
Si

F

F

Me
CF2 H

H
Me

CF2
Si

CF2
CF2

CF2 H Me

Si

CF2 CF2 H

H
Me

CF2 CF2 H

Geyer, A.M.; Haszeldine, R.N. J. Chem. Soc. 1957, 1038
Menapace, L.W.; Kuivila, H.G. J. Am. Chem. Soc. 1964, 86, 3047
Walling, C.; Cooley, J.H.; Ponaras, A.A.; Racah, E.J. J. Am. Chem. Soc. 1966, 88, 5361
Bennett, S.W.; Eaborn, C.; Hudson, A.; Hussain, H.A.; Jackson, R.A. J. Organometallic Chem 1969, 16, P36
Bennett, S.W.; Eaborn, C.; Hudson, A.; Jackson, R.A.; Root, K.D.J. J. Chem. Soc. A 1970, 348
Krusic, P.J.; Kochi, J.K. J. Am. Chem. Soc. 1969, 91, 3938

163
(iPr)3 Si

.

(tBu)3 Si

.

Jackson, R.A.; Weston, H. J. Organometallic Chem. 1984, 277, 13 (ESR)

2 tBuO

tBuO-OtBu

.

.

tBuO + (Me3 Si)3 SiH

.
.

O

(Me3 Si)3 Si
O

+ RNO2

R

N
R

N

Si(SiMe3) 3
O

(Me3 Si)3 SiO

.

+ (Me3 Si)3 SiH

.

tBuOH + (Me3 Si)3 Si

.

Si(SiMe3) 3
O

R-N=O + (Me3 Si)3 SiO

.

(Me3 Si)3 SiOH + (Me3 Si)3 Si

.

Ballestri, M.; Chatgilialoglu, C.; Lucarini, M.; Pedulli, G.F. J. Org. Chem. 1992, 57, 948
(ii) Germyl
R1

.

Ge
R3

R2

Reviews:
Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1

164

2 tBuO

tBuO-OtBu
tBuO

.

Me3 Ge

Me3 Ge

+ Me3 GeH

.

.

.

+ tBuOH

Me3Ge

+

.

Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79
(iii) Stannyl
R1

.

Sn

R3

R2

Reviews:
Baines, K.; Dicke, R.; Neumann, W.P.; Vorspohl, K. NATO ASI Ser. Ser. C 1989, 260, 107
H3 Sn

.

Morehouse, R.L.; Christiansen, J.J.; Gordy, W. J. Chem. Phys. 1966, 45, 1751 (ESR, 4.2 K, Kr matrix)
Jackel, G.S.; Gordy, W. Phys. Rev. 1968, 76, 443
R'-CH=CH2 + R3 Sn

.

.

R'-CH-CH2 SnR3 + R3 Sn-H

.

R'-CH-CH2 SnR3
R'-CH2 -CH2 SnR3 + R3 Sn

.

Neumann, W.P.; Albert, H.J.; Kaiser, W. Tetrahedron Lett. 1967, 2041

:+

R2 Sn

R 2 Sn

:

R3 Sn

.

.

165

+

RSn

:

R = (Me3 Si)2 CH
Davidson, P.J.; Hudson, A.; Lappert, M.F.; Lednor, P.W. Chem. Commun. 1973, 829

2 tBuO

tBuO-OtBu
tBuO

.

nBu3 Sn

+ nBu3 SnH

.

.

nBu3 Sn

.

+ tBuOH

nBu3Sn

.

+

Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79
R3 Sn

.

R = (Me3 Si)2 CH

.

(R2 N)3 Sn
R = Me3 Si, tBu
Hudson, A.; Lappert, M.F.; Lednor, P.W. J. Chem. Soc. Dalton Trans. 1976, 2369

2 R3 Sn

R3 Sn-SnR 3

.

R3 Sn

S

+

S

.
R3 Sn
S

S

.

S

S

166

R3 Sn

.

S

R3 SnS

S

+

.

CH2 =CH 2 +
S

S

S

S

S

Forrest, D.; Ingold, K.U. J. Am. Chem. Soc. 1978, 100, 3868
R3 Sn

.

R = PhC(CH 3 )2 CH2 , Ph, Mes, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl
Lehnig, M.; Buschhaus, H.U.; Neumann, W.P.; Apoussidis, T. Bull. Soc. Chim. Belges 1980, 89, 907
iPr

iPr

Sn

Sn

iPr

3
iPr

iPr

iPr

2

iPr

Sn
3

3
iPr

iPr

Lehnig, M.; Apoussidis, T.; Neumann, W.P. Chem. Phys. Lett. 1983, 100, 189 (ESR)
Group V centred radicals (N, P)
Nitrogen centred radicals:
Reviews:
Nelsen, S.F. in Free Radicals (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 527
Michejda, C.J.; Campbell, D.H.; Sieh, D.H.; Koepke, S.R. ACS Symp. Ser. 1978, 69, 292
Miura, Y. Trends Org. Chem. 1997, 6, 197
Alfassi, Z.B. (ed.) N-Centered Radicals, Wiley: New York, 1998
(i) Aminyl

.

167

.
N

R1

R2

Reviews:
Danen, W.C.; Neugebauer, F.A. Angew. Chem. 1975, 87, 823

2 Ph2 NH

PbO2



Ph2 N-NPh2

2 Ph2 N

.

.

Ph3 C

Ph2 N-CPh 3

NO
Ph2 N-NO
Wieland, H. Ann. Chem. 1911, 381, 200
Wieland, H.; Gambajarin, S. Chem. Ber. 1906, 36, 1499
R1

2

R1

HgO
N

NH2

R1
N

N

N



R1

2

N

N

- N2

R2

R2

R2

.

R2

R1 = Me, R2 = Me; R1 = Me, R2 = Ph
Erusalimskii, B.L.; Dolgoplosk, B.A.; Kavunenko, A.P. Zh. Obshchei Khim. 1957, 27, 267; 301
R
O2N

N
O

OtBu

- CO2

O

Pedersen, C.J. J. Org. Chem. 1958, 23, 255

O2N

.

N

R

.

+ tBuO

168

.

NH2

NH

tBu

tBu

.

tBu

tBu

R

tBu

tBu

Atherton, N.M.; Land, E.J.; Porter, G. Trans. Faraday Soc. 1963, 59, 818
Ph

Ph
N

N

N

N

O

Ph



Ph

Ph
N

Cl


77 K
CCl4

O

N2 +

77 K
O CCl4

N
O

2

N

.

O

.

.

+ Cl

Johnston, K.M.; Williams, G.H.; Williams, H.J. Chem. Ind. 1966, 991
Johnston, K.M.; Williams, G.H.; Williams, H.J. J. Chem. Soc. Sect. B 1966, 1114

R2 N

N

N

NR2

N 2 + 2 R2 N

.

Kochi, J.K.; Krusic, P.J. J. Am. Chem. Soc. 1969, 91, 6161
Danen, W.C.; Kensler, T.T. J. Am. Chem. Soc. 1970, 92, 5235

169
tBu-O-O-tBu
NH

2 tBu-O

+ tBuO

.

.

tBuOH +

N

.

Danen, W.C.; Kensler, T.T. Tetrahedron Lett. 1971, 2247

.

N

tBu

Nelsen, S.F.; Landis, R.T.; Kiehle, L.H.; Leung, T.H. J. Am. Chem. Soc. 1972, 94, 1610

.

(ii) N-alkoxy-N-alkylamino radicals
N

R1

OH

Reviews:
None.
Ti+4 + OH- + HO

Ti+3 + H 2 O2

HO

.

R1

+
R2

R1

OH
N

.

HO

.
N

R2

R1

OH

Smith, P.; Fox, W.M. Can. J. Chem. 1969, 47, 2227

HO

O
NH

R2

.

170

.

O


R

N

O
NH

tBu

O

OtBu

R

Danen, W.C.; West, C.T. J. Am. Chem. Soc. 1971, 93, 5582
tBu-O-O-tBu
NH

2 tBu-O

+ tBuO
OtBu

R

R

.

.

.

+
OtBu

N

tBuOH +

N2 + 2 CH 3

CH3 -N=N-CH3
NH

.

.

OtBu

.
N

CH4 +

CH 3

R

R

OtBu

Danen, W.C.; West, C.T.; Kensler, T.T. J. Am. Chem. Soc. 1973, 95, 5716
(iii) Amido radicals
O
R2

.
N

R1

Reviews:
Goosen, A. South African J. Chem. 1979, 32, 37
O

O
Cl

R1

N
R2


R1

.
N

R2 +

Cl

.

R1
tBu
Me

R2
Me
tBu

171
Danen, W.C.; Gellert, R.W. J. Am. Chem. Soc. 1972, 94, 6853
O
OtBu

.

R

N

Koenig, T.; Hoobler, J.A.; Mabey, W.R. J. Am. Chem. Soc. 1972, 94, 2514
O

O
Br

CH3

+ e- (aq)

NH

CH3

O

NH

O

.

CH3

NH

CH3

OH

.

_

N

Fessenden, R.W. Chem. Lett. 1974, 29, 364

.

(iv) Hydrazyl
N

R1

.

+ Br-

R3
N
R2

Reviews:
Nelsen, S.F. ACS Symp. Ser. 1978, 69, 309

+ H+

CH3

N

.

172

.

PbO2

Ph
N

2 Ph2 N-NPh

2 Ph2 N-NHPh

.

N

Ph2 N

Ph3 C

NPh2

NO
Ph

Ph
Ph2 N

Ph

Ph2 N

N

N
NO

CPh3

Goldschmidt, S. Chem. Ber. 1920, 53, 44

Ph2 N

.
N

Cl

Goldschmidt, S.; Wolf, A.; Wolffhardt, E.; Drimmer, I.; Nathan, S. Ann. Chem. 1924, 437, 194
NO2Ph

NO2Ph

.

O2N

N

Ph

-O

NO2

N
N+

N

.

N

-O
NO2

NO2Ph

+

.. .
..
+

N

Ph
O2N

N

NO2

Turkevich, J.; Oesper, P.F.; Smyth, C.P. J. Am. Chem. Soc. 1942, 64, 1179 (dipole moment measurement)

_

Ph

173

.

Ph
Ar

N

N

Ar



+

N

Ar

Ar

N

Ph

Wan, J.K.S.; Hess, L.D.; Pitts, J.N. J. Am. Chem. Soc. 1964, 86, 2069
NO2Ph

NO2Ph
N

O2N

Ph

KMnO4
nBu4 N+ Br-

NH

.

O2N

N

NO2

NO2

Brown, K.C.; Weil, J.A. Can. J. Chem. 1986, 64, 1836

.

O
R1

P

R2

N

N
R2

R1

R1
OEt
Et
OEt
OPh
Et

R2
Me
Me
H, tBu
H, tBu
H, tBu

Tordo, P. NATO ASI Ser. Ser. C 1986, 189, 191
R

R
R
X

N

NH P
R

R

O

R

tBuO-OtBu
X
OEt


N

X = O, CH2 ; R = H, Me

N

R

OEt
R

.

O
P
OEt

OEt

N

Ph

174
Lucarini, M.; Pedulli, G.F. J. Org. Chem. 2000, 65, 2723
(v) Nitroxide radicals
R1

.

N+

O-

R2

Reviews:
Keana, J.F.W. Chem. Rev. 1978, 78, 37
Perkins, M.J. Adv. Phys. Org. Chem. 1980, 17, 1
Volodarsky, L.B.; Reznikov, V.A.; Ovcharenko, V.I. Synthetic Chemistry of Stable Nitroxides, CRC Press: Boca Raton, FL, 1994
OH

KNO2 + 2 KHSO 3

N

- KOH

K+ - O3 S

O-

KMnO4 or
PbO2
SO3 - K+

N+

K+ - O3 S

Fremy, E. Ann. Chim. Phys. 1845, 15[3], 408; 459
HN

HN

NH
NH
N
O

.

HN

NH

.

NH

NH

N+
O-

Piloty, O.; Schwerin, B.G. Chem. Ber. 1901, 34, 1870; 2354

.

NH

N+
O-

.

SO3 - K+

175
HN

HN

NH
N

NH

N
N+

N+

HN

.

N

NH

.

N

N+

N+

-O

O-

HN

NH

-O

O-

Piloty, O.; Vogel, W. Chem. Ber. 1907, 36, 1283
NH

HN

NH

N+

N+

N

.

.

O- -O

HN

. .

N

O

O

Niementowski, S. Chem. Ber. 1910, 43, 3012
Kuhn, R.; Blau, W. Ann. Chem. 1958, 615, 99
(vi) Thioaminyl radicals
S
R1

R2

.
N

Reviews:
Bassindale, A.R.; Ipey, J. in Chemistry of Sulphenic Acids and Their Derivatives, (S. Patai, ed.) Wiley: Chichester, 1990, p. 101
Miura, Y. Trends in Org. Chem. 1997, 6, 197
Miura, Y. Recent Res. Development Org. Chem. 1998, 2(Pt. 2), 251

176
tBu

.
N

S

Cl

tBu

Miura, Y.; Katsura, Y.; Kinoshita, M. Chem. Lett. 1977, 409

.
N

S

Miura, Y.; Asada, H.; Kinoshita, M.; Ohta, K. J. Phys. Chem. 1983, 87, 3450
Ph
Ph

.
N

S

R

R = alkyl, aryl

Ph

Miura, Y.; Isogai, M.; Kinoshita, M. Bull. Chem. Soc. Jpn 1987, 60, 3065

.

(vii) Sulfonamidyl radicals
R1

N

SO2

R2

Reviews:
Bassindale, A.R.; Iley, J.N. in Chemistry of Sulphonic Acids, Esters, and Their Derivatives (S. Patai, ed.) Wiley: Chichester, 1991, p. 197 - 247

177
O
K+ - O

S

O
O

O

O
NH2

S

O - K+

.

O

NH

NH

- K2 SO4 , - H2 SO4

SO2

SO2

SO2

Dewar, P.S.; Forrester, A.R.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 1 1972, 2862

.
N

tBu

OR

SO2

Teeninga, H.; Engberts, J.B.F.N. Rec. Trav. Chim. Pays-Bas 1978, 97, 59
X

O
K+ - O

S
O

NHOMe
SO2

O

O

S

O - K+

.

O

- K2 SO4 , - H2 SO4

X

X

O

N-OMe

SO2

Forrester, A.R.; Johansson, E.M.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 1 1979, 1112

N-OMe
SO2

178
Y
RSO 2

N

RSO 2
Br

Y

.

tBuO

N

RSO 2

Y = alkyl, alkoxy

N

- tBuOH
H

.

tBu

tBu

tBuO
RSO 2

.

Y



N

RSO 2

- tBuOH
H

.

.

RSO2 +

N

O

tBu-N=O

R

R


MeSO2

N

- Cl
Cl

.

MeSO2

.

N

R = Me, Et, CHMe2

Danen, W.C.; Gellert, R.W. J. Am. Chem. Soc. 1980, 102, 3264

.

(viii) N-Thiosulfonamidyl radicals
R1

N

SO2

Reviews:
None.

R2
S

N
RSO 2

Teeninga, H.; Zomer, B.; Engberts, J.B.F.N. J. Org. Chem. 1979, 44, 4717

.
tBu

179
SAr



SO2 N
SAr

.

SAr

SO2 N
SAr

PbO2

SO2 N
H

Miura, Y.; Kunishi, T.; Kinoshita, M. J. Org. Chem. 1985, 50, 5862
Miura, Y.; Kunishi, T.; Kinoshita, M. Bull. Chem. Soc. Jpn. 1985, 58, 1696
(ix) Verdazyls
Reviews:
Power, P.P. Chem. Rev. 2003, 103, 789
Ph

Ph

MeI
PhNH

N

[O]
N

N

N-Ph

Ph

Ph
N
N

Ph
N

N

HN

N

Ph

Ph
N

N

N

N

.

N-Ph
Ph

Kuhn, R.; Trischmann, H. Angew. Chem. Int. Ed. 1963, 8, 155
Kuhn, R.; Trischmann, H. Monatsh. Chem. 1964, 95, 457
Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Monatsh. Chem. 1966, 97, 846

Ph

180
Ar1

O

Ar1

2

N

NH2

Ar2

+

Ar1

Ar1

2

Ar2

N

NH CH

Ar2

[O]

.

Ar1

2

Ar2

N

N

Ar1
CH

Ar2

Ar2

Ar1

Ar1
N

N

CH

Ar2

Ar2

2

Kuhn, R.; Neugebauer, F.A. Monatsh. Chem. 1963, 94, 1
Ar1

2

BF3
N

NH2

Ar1

Ar1

[O]

+ HC(OEt)3

N

Ar2

Ar1

N

CH

NH

Ar2

N

N
Ar2

N

Ar2

Ph
N
Ph

.
N

N

Ph

H

N

.

(CH2) 4
N

H
Ph

N

N
N

Ph
N

Ph

N

N

N
Ph

.
N

Ph

Kuhn, R.; Fischer-Schwarz, G. Monatsh. Chem. 1966, 97, 517

N

.
N

N

Ar1
N
Ar2

Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Angew. Chem. Int. Ed. 1964, 3, 232
Kuhn, R.; Trischmann, H. Monatsh. Chem. 1966, 97, 554
Ph

CH

.

N
Ph

181

.

.

Ph

N

Ph

N

N

N

N

N

N

n

Ph

R1

N
N+

Ph

R1

R2

R2
R1
Ph

R1 =

Ph

Ph

.

N

N

N

N

Ph

N

.

R2 =

N
N
N

Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Monatsh. Chem. 1966, 97, 525
Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Angew. Chem. Int. Ed. 1965, 4, 72
Kurusu, Y.; Yoshida, H.; Okawara, M. Tetrahedron Lett. 1967, 3595
O

R3
R1

R1
N

N

N

N

R2

.

N+

N

Ph

R1

R1
N

N

N

N

.

R2

Neugebauer, F.A. Angew. Chem. Int. Ed. 1973, 12, 455

Ph

_

_

N

N

N

Ph

N
N

n

Ph

182
Neugebauer, F.A.; Fischer, H.; Siegel, R. Chem. Ber. 1988, 121, 815
Phosphorus centred radicals:
Reviews:
Bentrude, W.G. in Free Radicals, (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 595
Walling, C.; Pearson, M.S. Topics Phosphorus Chem. 1966, 3, 1
Cadogan, J.I.G. Adv. Free Radical Chem. 1967, 2, 203
Bentrude, W.G. Ann. Rev. Phys. Chem. 1967, 18, 283
(i) Phosphinoyl (phosphonyl, phosphono) radicals
O

.
P

R1

R2

Reviews:
Rachon, J. Pol. J. Environ. Studies 1996, 5, 62
O
RO

P
P

O



OR
OR

2
RO

OR

.

O

RO

P

P

O

P

OR

OR
RO

O

OR

R = Et, nPr, nBu
Michalski, J.; Stec, W.; Zwierzak, A. Chem. Ind. 1965, 345
O

.

O

R = NMe2 , Et, Me(CH 2 )5

P

R

R

.
P

EtO

Et

Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989

183

O

O

γ-rays
RO

P

OH

RO

P

OR

.

O
RO

OR

P

.

O-

R = Me, Et
Kerr, M.C.L.; Webster, K.; Williams, F. Molecular Physics 1973, 25, 1461
Geoffroy, M.; Ginet, L.; Lucken, E.A. Molecular Physics 1976, 31, 745
O

.
P

X

X

Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)
O
O
tBuO

OtBu

2 tBuO

O

.

+ 2 CO2

O
O
RO

P
OR

H

.

+ tBuO

O
RO

P

.

OR

+ tBuOH

184
O
RO

P

.

.

CN

CN

+
O

S-tBu

OR

P

S-tBu
OR

RO

Stella, L.; Merenyi, R.; Janousek, Z.; Viehe, H.G. J. Phys. Chem. 1980, 84, 304
O

O

O


P

R

Ph
R

Ph

O

.

O

.

R

+

N

O

+

.

.
P

Ph

Ph

O
N

O
R

O

.
P

Ph

Ph +

N

O

.

O
N

O

P

Ph

Ph

Baxter, J.E.; Davidson, R.S.; Hageman, H.J.; Overeem, T. Makromolec. Chem. Rapid Commun. 1987, 8, 311 (first nitroxide trapping of
phosphinoyl radicals)

185
O

O

C

P

O

. .


R1

R2

R1

+

C

R3
O

O

C

P

R2

R3
O


R1

O

P

OR2

R1

C

. .

O

+

OR3

P

OR2

OR3

Majima, T.; Schnabel, W. J. Photochem. Photobiol. A: Chem. 1989, 50, 31
Majima, T.; Konishi, Y.; Bottcher, A.; Kuwata, K.; Kamachi, M.; Schnabel, W. J. Photochem. Photobiol. A: Chem. 1991, 58, 239
O
O

Ph
Ph
Ar



Ph

. .
+

P

Ph
P

Ar
O

O
O
Ph
Ph

P

COOMe

.

R-X

Ph
X

Ph
P

COOMe
O

Sluggett, G.W.; McGarry, P.F.; Koptyug, I.V.; Turro, N.J. J. Am. Chem. Soc. 1996, 118, 7367
Weber, M.; Khudyakov, I.V.; Turro, N.J. J. Phys. Chem. A 2002, 106, 1938

186
Weber, M.; Turro, N.J. J. Phys. Chem. A 2003, 107, 3326
O

O

O

O


Ar

C

P

C

Ar

Ar

C

. .
+

R

O

O

P

C

Ar

R

.

O2

O-O

O

O

P

C

Ar

R

Ph-SH
- Ph-S

.

O

.

H

C

Ar

- Cl3 C

O

P

C

Ar

R

O

Br-CCl3
P

O

.

Br

O

O

P

C

.

R

R

CH2 =CHCOOR'

Ar

R'OOC

O

O

P

C

Ar

R
N+

N+

O

O

+ P

C

Ar

R

Jockusch, S.; Turro, N.J. J. Am. Chem. Soc. 1998, 120, 11773

+

.

N

N+

187
O
O

O

P

Ph

O

Ph

..

P

O

Ph

O
PPh2

Ph



Zhao, N.; Strehmel, B.; Gorman, A.A.; Hamblett, I.; Neckers, D.C. J. Phys. Chem. A 1999, 103, 7757
O

O


Ph

P

CH2 Ph

Ph

P

Ph

. .
+

CH2 -Ph

Ph

Zhao, N.; Neckers, D.C. J. Org. Chem. 2000, 65, 2145
(ii) Phosphinyl radicals

.
P

R1

R2

Reviews:
Bentrude, W.G. Ann. Rev. Phys. Chem. 1967, 18, 283
O

O
O
O

O
O

.

+ CO2 + CH 3

.

188

.
.
.
.

CH3

+ PCl3

R-CH=CH 2 +

CH3 -Cl +

.

PCl2

.
.

PCl2

.

R-CH-CH 2 -PCl2
R-CH-CH 2 -CHR-CH 2 -PCl2

R-CH-CH 2 -PCl2 + R-CH=CH2
R-CH-CH 2 -PCl2 + PCl3

R-CHCl-CH2 -PCl2 +

.

PCl2

R-CHCl-CH2 -CHR-CH 2 -PCl2 +

R-CH-CH 2 -CHR-CH 2 -PCl2 + PCl3

.

PCl2

Kharasch, M.S.; Jensen, E.V.; Urry, W.H. J. Am. Chem. Soc. 1945, 67, 1864
NC

N

N

.

2 NC

CN

- N2

NC

.

+ R2 P-H

+ R2 P

NC

H

R2 P

.
.

.

+ R2 P

.

R2 P

- R2 P

R2 P-H
R2 P

=
R2 P

.

+ R2 P

.

189

.

Pellon, J. J. Am. Chem. Soc. 1961, 83, 1915
P

R

R = Cl, Br

R

Andrews, L.; Frederick, D.L. J. Phys. Chem. 1969, 73, 2774 (IR spectra in solid Ar matrix)
Ph

.

Ph


P

2

P

Ph

Ph

Ph

P

Ph

Wong, S.K.M.; Wan, J.K.S. Spectrosc. Lett. 1970, 3, 135

.
P

R

R

R = NMe2 , Et, EtO, Me(CH2 )5

Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989
60

Co γ-rays

R3 P

.

.

R2 P +
R
77 K
R = H, iPr, OMe, SMe, Ph, Cl, SPr, SEt

Fullam, B.W.; Mishra, S.P.; Symons, M.C.R. J. Chem. Soc. Dalton Trans. 1974, 2145
Fullam, B.W.; Symons, M.C.R. J. Chem. Soc. Dalton Trans. 1975, 861

Ph3 P

Ph2 P

. .
+

Ph

Cook, W.T.; Vincent, J.S.; Bernal, I.; Ramirez, F. J. Chem. Phys. 1974, 61, 3479

190

tBu-O-O-tBu
R

2 tBuO
R

P

+ tBuO

P

.
R

.

tBuO

.

P

.

R
P

P

R
R

R

R

R

+
R

R

P
tBuO

R = OEt, NMe2
Griller, D.; Roberts, B.P.; Davies, A.G.; Ingold, K.U. J. Am. Chem. Soc. 1974, 96, 554
60

P(OR)3

Co γ-rays

.

P(OR)2 + RO

77 K

.

Kerr, C.M.L.; Webster, K.; Williams, F. J. Phys. Chem. 1975, 79, 2650

.

Cl
Me3Si

P
N

SiMe3

Na

Me3Si

N

P

SiMe3

N

N

SiMe3

SiMe3

- NaCl
SiMe3

SiMe3

Cl
Me3Si

P

SiMe3

Na

Me3Si

.
P

SiMe3

- NaCl
SiMe3

SiMe3

SiMe3

SiMe3

Gynane, M.J.S.; Hudson, A.; Lappert, M.F.; Power, P.P. Chem. Commun. 1976, 623

R

191
Gynane, M.J.S.; Hudson, A.; Lappert, M.F.; Power, P.P.; Goldwhite, H. J. Chem. Soc. Dalton Trans. 1980, 2428
Cowley, A.H.; Kemp, R.A. Inorg. Chem. 1983, 22, 547

.
P

CH3

CH3

Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)

.

Me3Si

P

.

Fe(CO)4
SiMe3

Me3Si

P

SiMe3

+ Fe(CO)5

+ Fe2 (CO)9
SiMe3

.

Me3Si

P

SiMe3

SiMe3

SiMe3

(CO) 3Co
SiMe3

Me3Si

Co(CO)3
P

SiMe3

+ Co2 (CO)8
SiMe3

SiMe3

SiMe3

SiMe3

Cowley, A.H.; Kemp, R.A.; Wilburn, J.C. J. Am. Chem. Soc. 1982, 104, 331
(iii) Phosphoranyl radicals
R
R

.

P
R

R

.
+ 2 CO

192
Reviews:
Bentrude, W.G. ACS Symp. Ser. 1978, 69, 321
Roberts, B.P. Adv. Free Radical Chem. 1980, 6, 225
Bentrude, W.G. Acc. Chem. Res. 1982, 15, 117
Bentrude, W.G. Reactive Intermediates 1983, 3, 199
R-S-H + P(OEt)3

R-SH + S=P(OEt) 3

.

Hoffman, F.W.; Ess, R.J.; Simmons, T.C.; Hanzel, R.S. J. Am. Chem. Soc. 1956, 78, 6414

Br2 CH + Br
Br3 CH

.

..

Ph3 P-CHBr 2

Ph3 P + Br 2 CH

.

.

+
[Ph3 P-CHBr 2 ]Br- + Br2 CH

Ph3 P-CHBr 2 + Br3 CH

Ramirez, F.; McElvie, N. J. Am. Chem. Soc. 1957, 79, 5829
R-S-S-R

.
.
. .

R-S

R-S

R-S-P(OEt)3

+ P(OEt)3

R-S-P(OEt)3

+ R

. .
.

2 R-S

R

+

S=P(OEt)3

R-S-R

Walling, C.; Rabinowitz, R. J. Am. Chem. Soc. 1957, 79, 5326
Walling, C.; Rabinowitz, R. J. Am. Chem. Soc. 1959, 81, 1243
Walling, C.; Basedow, O.H.; Savas, E.S. J. Am. Chem. Soc. 1960, 82, 2181
Buckler, S.A. J. Am. Chem. Soc. 1962, 84, 3093

193

.
.



2 tBuO

tBuO-OtBu
R3 P + tBuO

.

(RO)3 P + tBuO

.

R3 P-OtBu

.

(RO)3 P-OtBu

Krusic, P.J.; Mahler, W.; Kochi, J.K. J. Am. Chem. Soc. 1972, 94, 6033

tBu-O-O-tBu

2 tBuO

OR

+ tBuO

P
RO

.

.

OR

RO
tBuO

.

P

OR

.

tBu

OR

+ O

RO

P

OR

OR

R = Et, Me
Griller, D.; Roberts, B.P.; Davies, A.G.; Ingold, K.U. J. Am. Chem. Soc. 1974, 96, 554

.

OMe
MeO

P

OMe

OtBu

Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)
(iv) Thiophosphinoyl (phosphinothioyl) radicals
S

.
P

R1

R2

194

Reviews:
None.
S

S


R

P

Cl

R

P

.

+ Cl

.

R

S
R

R

.

P

S

+ tBu-N=O

R

R

P
R

O

.

N
tBu

Karlsson, H.; Lagercrantz, C. Acta Chem. Scand. 1970, 24, 3411
S

.
P

EtO

OEt

Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989
Group VI centred radicals (O, S, Se)
Oxygen centred radicals:
(i) Acetoxy (acetoxyl) radicals
O

R

.

O

Reviews:

195
None.
O
O
O
Ph

Ph

2

O

Ph

O

.

2 Ph
- CO2

.

O

Brodie, B.C. Ann. Chem. 1858, 108, 79
Hey, D.H. J. Chem. Soc. 1934, 1966
Waters, W.A. J. Chem. Soc. 1937, 113
Roberts, J.S.; Skinner, H.A. Trans. Faraday Soc. 1949, 45, 339
McDowell, C.A.; Thomas, J.H. J. Chem. Soc. 1949, 2208; 2217
Marcotte, F.B.; Noyes, W.A. Jr. J. Am. Chem. Soc. 1952, 74, 783
Volman, D.H.; Graven, W.M. J. Chem. Phys. 1952, 20, 919
Nicholson, A.J.C. J. Chem. Phys. 1952, 20, 1811
Norrish, R.G.W. Z. Elektrochem. Angew. Physik. Chem. 1952, 56, 705
Porter, G.B.; Benson, S.W. J. Am. Chem. Soc. 1953, 75, 2773
Nicholson, G.R.; Szwarc, M.; Taylor, J.W. J. Chem. Soc. 1954, 2767
Ausloos, P.; Steacie, E.W.R. Can. J. Chem. 1955, 33, 47
Farmer, J.B.; Lossing, F.P.; Marsden, D.G.H.; Steacie, E.W.R. J. Chem. Phys. 1955, 23, 1169
O



O

.

+ CH 3

O

.

CO +

CH3

.

.

(slow)

(fast)

Szwarc, M.; Taylor, J.W. J. Chem. Phys. 1955, 23, 2310

196

.
.

S

+

S

N

O
N
O

O

R

R

.

O

R

SR

+
N

O

.

O

R

Barton, D.H.R.; Crich, D.; Motherwell, W.B. Tetrahedron 1985, 41, 3901
(ii) Alkoxy radicals
R

O

.

Reviews:
Walling, C. Pure Appl. Chem. 1967, 15, 69
Griller, D.; Wayner, D.D.M. Pure Appl. Chem. 1989, 61, 717
Orlando, J.J.; Tyndall, G.S.; Wallington, T.J. Chem. Rev. 2003, 103, 4657
H+
Fe(CN)6 -4
O-OH

O

- Fe(CN)6

.

+ H2O

-3

Fordham, J.W.L.; Williams, H.L. J. Am. Chem. Soc. 1950, 72, 4465
Kharasch, M.S.; Fono, A.; Nudenberg, N. J. Org. Chem. 1950, 15, 763

197

O

O

O

O

. .
+

O

O

. .

Ph

+

O

O

Ph

Kharasch, M.S.; Fono, A.; Nudenberg, W. J. Org. Chem. 1951, 16, 105
Kharasch, M.S.; Nudenberg, N.; Arimoto, F.S. Science 1951, 113, 392 (addition to olefins)
Boardman, H. J. Am. Chem. Soc. 1953, 75, 4268

.

ROOH + Fe+2

RO + Fe+3

.

RO + Fe+2

RO- + Fe+3

Orr, R.J.; Williams, H.L. J. Am. Chem. Soc. 1955, 77, 3715

O

O

OH

.

+

Zwolenik, J.J. J. Phys. Chem. 1967, 71, 2464

O

O

OH

.

+ HO

.
O

O

.

+

OH

198

O

2

O

O

.

Niki, E.; Kamiya, Y.; Ohta, N. Bull. Chem. Soc. Jpn 1968, 41, 1466

O

.

O

+ CH 3

.

Howard, J.A.; Ingold, K.U. Can. J. Chem. 1969, 47, 3797
(iii) Iminoxyl radicals
R1

O

.

N
R2

Reviews:
Rozantsev, E.G. Usp. Khim. 1966, 35, 1549
R1

OH

K3 [Fe(CN)6 ]

R1

N
R2

O
N

or PbO2
or AgO

R2

Fedtke, M.; Mitternacht, H. Z. Chem. 1964, 4, 389

.

R1
t-Bu
i-Pr
i-Bu

R2
Me
i-Pr
i-Pr

β-scission

199
R1

R1

OH

O

Pb(OAc)4

.

N

N
R2

R2

Lemaire, H.; Rassat, A. Tetrahedron Lett. 1964, 2245
R1

OH

R1

O

Ce(NO3 )4

.

N

N

NH 4 (NO3 )
R2

R2

.

Thomas, J.R. J. Am. Chem. Soc. 1964, 86, 1446
R1

OH

R1

PbO2

O
N

N
R2

R2

Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. (Phys. Org.) 1966, 86
N
OH

O

.

OH

O

N

NO

N

Pb(OAc)4
Ar

N

Pb(OAc)4

Ar

Ar
OAc

.
_

.

200

Lown, J.W. J. Chem. Soc. B 1966, 441
R

OH

R

OH

N

+ Br2 NH

N

.
+

R

O

.

N

.

+ H+
- 2 Br-

NH

NH

Everett, S.A.; Naylor, M.A.; Stratford, M.R.L.; Patel, K.B.; Ford. E.; Mortensen, A.; Ferguson, A.C.; Vojnovic, B.; Wardman, P. J. Chem. Soc.
Perkin Trans. 2 2001, 1989
(iv) Nitroxyl radicals
O

.

N
R1

R2

Reviews:
Rozentsev, E.G. Free Nitroxyl Radicals, (translated by B.J. Hazzard) Plenum: New York, 1970
Rozantsev, E.G.; Sholle, V.D. Synthesis 1971, 190
Rozantsev, E.G.; Sholle, V.D. Synthesis 1971, 401
Volodarsky, L.B.; Reznikov, V.A.; Ovcharenko, V.I. Synthetic Chemistry of Stable Nitroxides, CRC Press: Boca Raton, FL, 1994
OH

O

H2 O
Ar1

N

O

+ Ar2 -MgX

- HOMgX Ar
1

.

[O]
N

N
Ar2

Ar1

Ar2

201
O
R

.

N

R

Wieland, H.; Roseeu, A. Chem. Ber. 1912, 45, 494
Wieland, H.; Offenbächer, M. Chem. Ber. 1914, 47, 2111
Wieland, H.; Roseeu, A. Chem. Ber. 1915, 48, 1117
Wieland, H.; Roth, K. Chem. Ber. 1920, 53, 210
Wieland, H.; Kögel, F. Chem. Ber. 1922, 55, 1798
OR

1. HNO3 /H2 SO4
O-

2. HClO4
2

+

N+

RO

Zn

OR

ClO4 ORO

N

OR

Meyer, K.H.; Gottlieb-Billroth, H. Chem. Ber. 1919, 52, 1476
Meyer, K.H.; Reppe, W. Chem. Ber. 1921, 54, 327
HO
NO

.

Ph
N

O

Ph

PhMgBr

N

Hückel, W.; Liegel, W. Chem. Ber. 1938, 71, 1442

[O]

202
Johnson, D.; Rogers, M.; Trappe, G. J. Chem. Soc. 1956, 1093 (postulated existence of free nitroxyl radicals)
Rogers, M. J. Chem. Soc. 1956, 2784
NH

HN

NH

N+

N+

N

.

.

HN

. .

N

O

O- -O

O

Niementowski, S. Chem. Ber. 1910, 43, 3012
Kuhn, R.; Blau, W. Ann. Chem. 1958, 615, 99

N

O

.

Lebedev, O.L.; Kazarnovskii, S.N. Treatises on Chemistry and Chemical Technology, Gorky, 1959, 3, 649
Il'yasov, A.V. Zh. Strukt. Khim. 1962, 3, 95
Garif'yasov, I.S.; Il'yasov, A.V.; Yablokov, Yu. V. Dokl. Akad. Nauk SSSR 1963, 149, 876
tBu
N

.

O

tBu

N

N

R



N2 + 2 R

.

R

203
tBu

.

+

.

R

N

tBu-N=O

O

R

Hoffmann, A.K.; Henderson, A.T. J. Am. Chem. Soc. 1961, 83, 4671
Hoffmann, A.K.; Hodgson, W. J. Am. Chem. Soc. 1961, 83, 4675
Hoffmann, A.K.; Hodgson, W.; Maricle, D.; Jura, W. J. Am. Chem. Soc. 1964, 86, 631
Hoffmann, A.K.; Feldman, A.; Gelblum, E.; Hodgson, W. J. Am. Chem. Soc. 1964, 86, 639
Hoffmann, A.K. FR 1,357,477 (1964)
Hoffmann, A.K. US 3,253,015 (1966)

.

O

N

N

O

.

Rozantsev, E.G.; Golubev, V.A.; Neiman, M.B. Izv. Akad. Nauk SSSR, Ser. Khim. 1965, 393
O

.

N

(CH2) 6
N

.

+ 2

N

C

O

O
N

O

O

C

O

(CH2) 6

O

O
OH

HN

O

NH

NH

NH

N

MnO2

.

NH

O

NH

O
N

O

NH

N

NH

.

O

.

204

Rozantsev, E.G.; Golubev, V.A.; Neiman, M.B.; Kokhanov, Yu.V. Izv. Akad. Nauk SSSR, Ser. Khim. 1965, 572

R

N

.
O

R = H, OH, O=, =NOH, OAc

Briere, R.; Lemaire, H.; Rassat, A. Bull. Soc. Chim. Fr. 1965, 3273
O
NH

[O]

.

N

Rozantsev, E.G. Usp. Khim. 1966, 35, 1549
O

O

[O]
NH

N
O

.

Rozantsev, E.G. Izv. Akad. Nauk SSSR, Ser. Khim. 1966, 770
Rozantsev, E.G.; Neiman, M.B. Tetrahedron 1964, 20, 131

205
O

[O]

NH
R1

.

N

R2

R1

R2

Lebedev, O.L.; Khidekel, M.L.; Razuvaev, G.A. Dokl. Akad. Nauk SSSR 1961, 140, 1327
Rozantsev, E.G.; Neiman, M.B. Tetrahedron 1964, 20, 131
Rozantsev, E.G.; Krinitzkaya, L.A. Tetrahedron 1965, 21, 491
Rozantsev, E.G.; Burmistrova, R.M. Dokl. Chem. 1966, 166, 38
Rozantsev, E.G.; Kokhanov, Yu.V. Bull. Acad. Sci. USSR 1966, 1422
R

RMgX

[O]

R

R'MgX
R

N+

N+

O-

OH

H

N+

N

O-

OH

R'

Bonnett, R.; Brown, R.F.C.; Clark, V.M.; Sutherland, I.O.; Todd, A. J. Chem. Soc. 1959, 2094
Brown, R.F.C.; Clark, V.M.; Lamchen, M.; Todd, A. J. Chem. Soc. 1959, 2116
Keanu, J.F.W.; Lee, T.D.; Bernard, E.M. J. Am. Chem. Soc. 1976, 98, 3052
(v) Kenyon-Banfield radical
-O

O

Ph
N+
O
N
Ph

.

N
Ph

.
O

Ph
N

R

[O]
N
O

.

R'

206
CH2 -

Ph
N+
O
NH
Ph

Ph

+
OH

- H2 O

OH
Ph

-O
N+

-O

.

O

N

[O]

Ph

Ph

N

Ph
N+

N+

-O

-O

Banfield, F.H.; Kenyon, J. J. Chem. Soc. 1926, 1612
Baldry, P.J.; Forrester, A.R.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 2 1976, 76
(vi) Peroxy radicals
O
R

O

.

Reviews:
Ingold, K.U. Acc. Chem. Res. 1969, 2, 1
Swern, D. (ed.) Organic Peroxides, Wiley-Interscience: New York, Vol. 1 - 3, 1970 - 1981
Ando, W. (ed.) Organic Peroxides, Wiley: New York, 1992
Alfassi, Z.B. (ed.) Peroxyl Radicals, Wiley: New York, 1997
Foner, S.N.; Hudson, R.L. J. Chem. Phys. 1953, 21, 1608 (detection of hydroperoxide radical)

207

O

O

.

Bersohn, M.; Thomas, J.R. J. Am. Chem. Soc. 1964, 86, 959 (detection by ESR)

O

O

OH

.

O

+

O

.

OH

+ HO

.
O

O

.

+

OH

Zwolenik, J.J. J. Phys. Chem. 1967, 71, 2464
Howard, J.A.; Ingold, K.U. Can. J. Chem. 1969, 47, 3797
(vii) Phenoxy (phenoxyl) radicals

.

O

R

Reviews:
Becconsall, J.K.; Clough, S.; Scott, G. Trans. Faraday Soc. 1960, 56, 459 (ESR of phenoxy radicals)
Müller, E. Revista Portuguesa de Quimica 1972, 14, 129
Iley, J.; Taylor, P.G. in The Chemistry of Hydroxyl, Ether Peroxide Groups, (S. Patai, ed.) Wiley: Chichester, 1993, p. 241
Prokof'ev, A.I. Russ. Chem. Rev. 1999, 68, 727
2 ArO- Na+ + I2

.

2 ArO + 2 NaI

208
Müller, E.; Ley, K.; Kiedaisch, W. Chem. Ber. 1954, 87, 1605
Hunter, W.H.; Seyfried, L.M. J. Am. Chem. Soc. 1921, 43, 151
t-Bu

t-Bu

K3 [FeIII(CN)6 ]
HO

t-Bu

.

O

t-Bu

t-Bu

t-Bu

Müller, E.; Ley, K. Z. Naturforsch. 1953, 8B, 694
Müller, E.; Ley, K. Chem. Ber. 1954, 87, 922
Müller, E.; Ley, K.; Kiedaisch, W. Chem. Ber. 1954, 87, 1605
Müller, E.; Ley, K. Chem. Ber. 1955, 88, 601
Cook, C.D. J. Am. Chem. Soc. 1953, 18, 261
Cook, C.D.; Kuhn, D.A.; Fianu, P. J. Am. Chem. Soc. 1956, 78, 2002
Blanchard, H.S. J. Org. Chem. 1960, 25, 264
O

.

Ph

OH

OH
Ph

tBu

tBu

Ph

Ph

.

tBu

tBu

+

+

Ph

O

tBu

Ph

Dimroth, K.; Kalk, F.; Sell, R.; Schlömer, K. Ann. Chem. 1959, 624, 51

tBu

209
tBu

tBu

tBu

tBu

PbO2
HO

CH2

OH

tBu

ether

O

tBu

CH

tBu

Coppinger, G.M. J. Am. Chem. Soc. 1957, 79, 501
Joshi, B.S. Chem. Ind. 1957, 525
Bartlett, P.D.; Funahashi, T. J. Am. Chem. Soc. 1962, 84, 1605
ESR:
Besev, C.; Lund, A.; Vanngard, T.; Hakansson, R. Acta Chem. Scand. 1963, 17, 2281
Hyde, J.S. J. Chem. Phys. 1965, 43, 1806
Hausser, K.H.; Brunner, H.; Jochims, J.C. Mol. Phys. 1966, 10, 253
O

.

O

tBu

tBu

O

.

Yang, N.; Kastro, A. J. Am. Chem. Soc. 1960, 82, 6208

O

tBu

.

210
O

OH

.

tBu tBu

tBu

O
tBu

.

OH
tBu tBu

tBu

tBu

+

+

tBu

tBu

tBu

tBu

Kreilick, R.W.; Weissman, S.I. J. Am. Chem. Soc. 1962, 84, 306
OH

O

.

tBu

tBu

tBu

O

tBu

H

R2

-H

.

O
tBu
R1

R1

R2

.
.

OH

O

- tBu

R1

Matsuura, T.; Nishinaga, A.; Cahnmann, H.J. J. Org. Chem. 1962, 27, 3620
H2 O2 / Ti+2
PhOH

PhO

.

Dixon, W.T.; Norman, R.O.C. Proc. Chem. Soc. 1963, 97 (ESR of phenoxy radical)

R2

211
NMe2

tBu

.

O

N

tBu

NMe2

Neuhoeffer, O.; Heitmann, P. Chem. Ber. 1963, 96, 1027
I

.

HO
COOH

O

I

Matsuura, T.; Kon, H.; Cahnmann, H.J. J. Org. Chem. 1964, 29, 3058

.

CH3 + HOPh

CH4 + PhO

.

Mulcahy, M.F.R.; Williams, D.J. Austr. J. Chem. 1965, 18, 20

212
NO2

.

tBu

N
NPh2

O2N

.

O

NO2

OH

NPh2

+
O2N

NO2

NO2

Ayscough, P.B.; Russell, K.E. Can. J. Chem. 1967, 45, 3019
O

.

tBu

OH
tBu

.

OH
tBu

O
tBu

+

+
R

tBu
O

.

tBu

R
tBu

.

O

O

tBu

tBu

tBu

+
R

tBu

NH

tBu

tBu

O

tBu

Mahoney, L.R.; DaRooge, M.A. J. Am. Chem. Soc. 1970, 92, 890

+

tBu

213
OH

O

tBu

tBu

1/4 PbO2

.

tBu

tBu

- 1/4 Pb
- 1/2 H2 O
Stebbins, R.; Silicio, F. Tetrahedron 1970, 26, 291
Sulfur centred radicals:
Reviews:
Kice, J.L. in Free Radicals, (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 711
Davies, D.L.; Parrott, M.J. in Int. Rev. Sci.: Org. Chem. Ser. 2 Butterworth: London, 1975, Vol. 10, p. 47
Asmus, K.D. NATO ASI Ser. A 1990, 197, 155
Griller, D.; Simoes, J.A.M. NATO ASI Ser. A 1990, 197, 327
Alfassi, Z.B. (ed.) S-Centered Radicals, Wiley: New York, 1999
(i) Sulfanyl (mercapto, thiyl) radicals
R

S

.

Reviews:
Kooijman, E.C. Pure Appl. Chem. 1967, 15, 81
Kellogg, R.M. Methods in Free Radical Chem. 1969, 2, 1
Ito, O. Trends Phys. Chem. 1992, 3, 245
Chatgilialglu, C.; Guerra, M. The Chemistry of Sulphur Containing Functional Groups, (Z. Rappoport, ed.) Wiley: Chichester, 1993, p. 363
Ito, O. Res. Chem. Intermediates 1995, 21, 69

S
R

.

R = H, p-MeO, p-Me2 N, p-COOEt, p-Ph, o-OH

214
Schmidt, U.; Müller, A.; Markau, K. Tetrahedron Lett. 1963, 1091

2 tBuO

tBuO-OtBu
tBuO

.

MeS

.
MeS

+ MeSH

.

.

+ tBuOH

MeS

+

.

Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79

2 R'-S

R'-S-S-R'
S

.

+ R'-S
R

R

.
.
R

S

S-R'

R

Alberti, A.; Bonini, B.F.; Pedulli, G.F. Tetrahedron Lett. 1987, 28, 3737
(ii) Sulfinyl radicals
O
R

S

.

Reviews:
Chatgilialoglu, C. in Chemistry of Sulphones and Sulfoxides, (S. Patai, Z. Rappoport, C. Stirling, eds.) Wiley: New York, 1988, p. 1081 - 1087

215

.

Ar-S-S-Ar + HO

.

Ar-S(O)Cl

Ar-S
- H2 O



.

Ar

.

Ar-SH + HO

.

OH

.
.

Ar-S=O

.
S

SAr

H2 O2

+ Cl

Ar-S=O

- H+
- ArS-

. .

HO
Ar-S-OH

Ar-S=O

.

Gilbert, B.C.; Kirk, C.M.; Norman, R.O.C.; Laue, H.A.H. J. Chem. Soc. Perkin Trans. 2 1977, 497
R-S + O2

.

R-S-O-O

R-S=O + other products
NH2

NH2
NH

HS
COOH

cysteine

HS

COOH
O
O

NH

COOH

glutathione
Sevilla, M.D.; Becker, D.; Swarts, S.; Herrington, J. Biochem. Biophys. Res. Commun. 1987, 144, 1037
Becker, D.; Swarts, S.; Champagne, M.; Sevilla, M.D. Int. J. Radiat. Biol. 1988, 53, 767

216

.

2 RSO2 -Cl

O

2 RSO2

R

.

.

O

S

O

S

O

R

. .

.

R-S=O + R-SO2 -O
O

O

2 R-S=O

R

S

O

. .

R-SO2 -O

+

S
O

RSO2

R

RS

R
O

S

O

O

S

+ RSO2

R

S

S

R

O
R

O

R = Ph

.
.

.

Bennett, J.E.; Brunton, G.; Gilbert, B.C.; Whittall, P.E. J. Chem. Soc. Perkin Trans. 2 1988, 1359

R'-S

+ O2

.

R'-S-O-O

.

R-OOH + R'-S

R-OO + R'-SH

R'-S-O-O

+ R'-SH

.

R'-S=O

+ R'S-OH

Swarts, S.G.; Becker, D.; De Bolt, S.; Sevilla, M.D. J. Phys. Chem. 1989, 93, 155 (gamma irradiation in Cl2 FC-CF 2 Cl at 77 K; ESR of radicals)
(iii) Sulfonyl radicals
O
R

S

.

O

Reviews:

217
Freeman, F.; Keindl, M.C. Sulfur Reports 1985, 4, 231
Chatgilialoglu, C. in The Chemistry of Sulphones and Sulphoxides, (S. Patai, Z. Rappoport, C. Stirling, eds.) Wiley: Chichester, 1988, p. 1089
Bertrand, M.P. Org. Prep. Proced. Inter. 1994, 26, 257
Crich, D. in Organosulfur Chemistry, (P. Page, ed.) Academic Press: London, 1995, p. 49

tBu-O-O-tBu

2 tBu-O

.
.

.

tBuOH + Et3 Si

tBu-O + Et3 SiH

.

.

Et3 Si-Cl + Ph-SO2

Et3 Si + Ph-SO2 Cl

Chatgilialglu, C.; Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. Perkin Trans. 2 1979, 770
Chatgilialglu, C.; Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. Perkin Trans. 2 1980, 1429
Bennett, J.E.; Brunton, G.; Gilbert, B.C.; Whittall, P.E. J. Chem. Soc. Perkin Trans. 2 1988, 1359
(iv) Sulfuranyl radicals
R1

.
S

R2

R3

Reviews:
Anklam, E.; Margaretha, P. Res. Chem. Intermed. 1989, 11, 127
Chatgilialoglu, C. in Chemistry of Sulphenic Acids and Their Derivatives (S. Patai, ed.) Wiley: Chichester, 1990, p. 549 - 569
Margaretha, P. in S-Centered Radicals (Z.B. Alfassi, ed.) Wiley: Chichester, 1999, p. 277 - 288

RO-Cl

.

RO

+ SF4

. .
.

RO

+

Cl

RO-SF4

218
Gregory, A.R.; Karavelas, S.E.; Morton, J.R.; Preston, K.F. J. Am. Chem. Soc. 1975, 97, 2206
OMe

MeO

.

.

S

+

S

MeO

OMe

MeO

OMe

Cooper, J.W.; Roberts, B.P. Chem. Commun. 1977, 228
O-SiMe3

.

R

Me3 Si-O

.

R

S

R

S

R

R

R

+
R

R

R

Me3 Si-OH +

.

S

R

R

R

Gara, W.B.; Roberts, B.P. J. Organometallic Chem. 1977, 135, C20
O-CMe3
R

Me3 C-O

.

+ R

S

.
S

R

R

Me3 C-OH + R

.

S

R

Gara, W.B.; Giles, J.R.M.; Roberts, B.P. J. Chem. Soc. Trans. Perkin 2 1979, 1444

219

SMe

SMe


O

tBu
O

.

.

O

- tBuO

O

O

S

.
O

O

Perkins, C.W.; Martin, J.C.; Arduengo, A.J.; Lau, W.; Alegria, A.; Kochi, J.K. J. Am. Chem. Soc. 1980, 102, 7753
Nakanishi, W.; Kusuyama, Y.; Ikeda, Y.; Iwamura, H. Bull. Chem. Soc. Jpn. 1983, 56, 3123

CF3 S

S-CF3

.
S

O
Et

S
O

tBu

S

.
S

R1

.
.

R1

R2

S(CO)Et

R2

.
S

R1

R2

S(CO)tBu

.
S

R1

R2

Giles, J.R.M.; Roberts, B.P. J. Chem. Soc. Perkin Trans. 2 1980, 1497
(v) Thionitroxide radicals
R1
N
R2

S

.

220

Reviews:
None.


N

S

S

2

N

N

S

.


O

N

S

S

N

2 O

O

N

S

.

Bennett, J.E.; Sieper, H.; Tavs, P. Tetrahedron 1967, 23, 1697


N

S

S

2

N

-O

N

S

.

Ph
N+

N

S

S

N

+
O

.

N

S

.

-O

Ph
N+

+

O

N

N

Ph

Ph

Danen, W.C.; Newkirk, D.D. J. Am. Chem. Soc. 1976, 98, 516

N
S

221


N

S

S

2

N

N

S

.

Maillard, B.; Ingold, K.U. J. Am. Chem. Soc. 1976, 98, 520
(vi) Thiophenoxy (phenylthio, phenylthiyl, benzenethiyl) radicals

.

S
R

Reviews:
None.
X
S

S
S



.

2
X

X

X = H, MeO, Me2 N, OH, EtOOC, Ph
Schmidt, U.; Müller, A.; Markau, K. Chem. Ber. 1964, 97, 405
Selenium centred radicals:
Reviews:
Deryagina, E.N.; Voronkov, M.G.; Korchevin, N.A. Usp. Khim. 1993, 62, 1173
Deryagina, E.N.; Voronkov, M.G. Sulfur Reports 1995, 17, 89

222

(i) Phenylselanyl (phenylseleno) radical

Se

.

Reviews:
None.
Schmidt, U.; Müller, A.; Markau, K. Tetrahedron Lett. 1963, 1091 (ESR)
Se
Ph

Ph


2 PhCH 2 Se

Se
Se

Ph



Ph

2 Ph-Se

Se

.

.

Schmidt, U.; Müller, A.; Markau, K. Chem. Ber. 1964, 97, 405
Ph-Se-Se-Ph

.

2 Ph-Se

Ph-Se + R-CH=CH2

.

R-CH-CH 2 -SePh

+ O2

..

R-CH-CH 2 -SePh

.

R-C(OO )H-CH2 -SePh

Ito, O. J. Am. Chem. Soc. 1983, 105, 850

223
Ph-Se-Se-Ph
Ph-Se

.

2 Ph-Se

+ R

.

PhSe

COOMe

PhSe

.

COOMe
R
PhSe

COOMe

PhSe

R

.
COOMe

SePh

Ph-Se-Se-Ph
- Ph-Se

.

R

SePh

R

COOMe

Back, T.G.; Krishna, M.V. J. Org. Chem. 1988, 53, 2533
(ii) Selanyl
R

Se

.

Reviews:
None.
Ph3 Se-X

X-irradiation

.

Ph2 Se-X +

Ph

.

X = Cl, Br

Franzi, R.; Geoffroy, M.; Ginet, L.; Leray, N. J. Phys. Chem. 1979, 83, 2898
Radical Anions
Reviews:
Kaiser, E.T.; Kevan, L. (eds.) Radical Anions, Interscience Publishers: New York, 1968
Szwarc, M. Prog. Phys. Org. Chem. 1968, 6, 323
Melby, L.R. in The Chemistry of the Cyano Group (Z. Rappoport, ed.) Wiley-Interscience: London, 1970. Vol. 2, p. 639
Russell, G.A.; Norris, R.K. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 423
Rossi, R.A. Acc. Chem. Res. 1982, 15, 164
Hertler, W.R.; Mahler, W.; Melby, L.R.; Miller, J.S.; Putscher, R.E.; Webster, O.W. Molecular Crystals & Liquid Crystals 1988, 171, 205
Saveant, J.M. Adv. Phys. Org. Chem. 2000, 35, 117

224
Rathore, R.; Kochi, J.K. Adv. Phys. Org. Chem. 1998, 31, 193
Webster, O.W. J. Polym. Sci. A 2002, 40, 210 (tetracyanoethylene radical anion)
Todres, Z.V. Organic Ion Radicals, Marcel Dekker, Inc.: New York, 2003
_
K
K
K+

.

Berthelot, M. Compt. Rend. 1866, 63, 836
Berthelot, M. Ann. Chim. Phys. 1867, 12, 1955

.
_

Na

Na+

Schlenk, W.; Appenrodt, J.; Michael, A.; Thal, A. Chem. Ber. 1914, 47, 473
Weitz, E.Z. Z. Elektrochem. 1928, 34, 538
Willstätter, R.; Seitz, F.; Bumm, E. Chem. Ber. 1928, 61, 871
Schlenk, W.; Bergmann, E. Ann. Chem. 1928, 463, 1; 1928, 464, 1
Scott, N.D.; Walker, J.F.; Hansley, V.L. J. Am. Chem. Soc. 1936, 58, 2442
Walker, J.F.; Scott, N.D. J. Am. Chem. Soc. 1938, 60, 951
Hueckel, W.; Bretschneider, H. Ann. Chem. 1939, 540, 157
Lipkin, D.; Paul, D.E.; Townsend, J.; Weissman, S.I. Science 1953, 117, 534
Weissman, S.I.; Townsend, J.; Paul, D.E.; Pake, G.E. J. Chem. Phys. 1953, 21, 2227
Wertz, J.E.; Vivo, J.L. J. Chem. Phys. 1955, 23, 2441
NC

CN

NC

CN

+A
NC

CN

NC

CN

.
_

+ A+

.

-2
2 K+

225
Webster, O.W.; Mahler, W.; Benson, R.E. J. Org. Chem. 1960, 25, 1470
Webster, O.W.; Mahler, W.; Benson, R.E. J. Am. Chem. Soc. 1962, 84, 3678
Phillips, W.D.; Rowell, J.C.; Weissman, S.I. J. Chem. Phys. 1960, 33, 626 (ESR spectrum)
NC

CN

NC

CN

.
_

Acker, D.S.; Hertler, W.R. J. Am. Chem. Soc. 1962, 84, 3770
_
tBu-NO2
tBu-NO2 + etBu-NO2
tBu-NO2

.
.
_

_

NO2 - + tBu

.
.
. .
+ tBu

tBu-N=O + tBu
(tBu)2 N-O

.
.

+ tBu

tBu-N=O + tBuO(tBu)2 N-O

.

(tBu)2 N-OtBu

Hoffmann, A.K.; Hodgson, W.G.; Jura, W.H. J. Am. Chem. Soc. 1961, 83, 4675
Radical Cations
Reviews:
Michaelis, L. Chem. Rev. 1935, 16, 243
Kaiser, E.T.; Kevan, L. (eds.) Radical Ions, Interscience Publishers: New York, 1968
Szwarc, M. Prog. Phys. Org. Chem. 1968, 6, 323
Ledwith, A. Acc. Chem. Res. 1972, 5, 133
Russell, G.A.; Norris, R.K. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 423
Bard, A.J.; Ledwith, A.; Shine, H.J. Adv. Phys. Org. Chem. 1976, 13, 156
Bard, A.J.; Faulkner, L.R. Electrochemical Methods, Wiley: New York, 1980
Mattes, S.L.; Farid, S. Org. Photochem. 1983, 6, 233

226
Yoshida, K. Electro-oxidation in Organic Chemistry, Wiley: New York, 1984
Hammerich, O.; Parker, V.D. Adv. Phys. Org. Chem. 1984, 20, 55
Mattay, J. Angew. Chem. Int. Ed. 1987, 26, 825
Roth, H.D. Top. Curr. Chem. 1992, 163, 131
Eberson, L. Adv. Phys. Org. Chem. 1998, 31, 91
Saveant, J.M. Adv. Phys. Org. Chem. 2000, 35, 117
Rathore, R.; Kochi, J.K. Adv. Phys. Org. Chem. 1998, 31, 193
Werst, D.W.; Trifunac, A.D. Acc. Chem. Res. 1998, 31, 651
Todres, Z.V. Organic Ion Radicals, Marcel Dekker, Inc.: New York, 2003
Wiest, O.; Oxgaard, J.; Saettel, N.J. Adv. Phys. Org. Chem. 2003, 38, 87

Ph2 NH

H2 SO4

.
+

Ph2 NH

Laurent, A. Ann. Chim. Phys. 1835, 59, 367
Laurent, A. Ann. Chem. Phys. 1836, 17, 89

.

Wurster salts

+
[O]

H2 N

Me2N

NH2

- e-

NMe2

H2 N

- e-

Me2N

NMe2

Wurster's blue
Me2N

NH2

+ Br-

.

+ Br-

+

Br2
HOAc

.
+

Br2
HOAc

[O]

NH2

Me2N

NH2

Wurster's red

+
H2 N

+
NH2

227
Baeyer, A. Chem. Ber. 1875, 8, 614
Wurster, C. Chem. Ber. 1879, 12, 522
Wurster, C.; Sendtner, R. Chem. Ber. 1879, 12, 1803
Wurster, C.; Schobig, E. Chem. Ber. 1879, 12, 1807
Wurster, C. Chem. Ber. 1879, 12, 2071
Wurster, C., Chem. Ber. 1886, 19, 3195
Willstätter, R.; Piccard, J. Chem. Ber. 1908, 41, 1458
Piccard, J. Chem. Ber. 1911, 46, 1843
Michaelis, L. J. Am. Chem. Soc. 1931, 53, 2953
Katz, H. Z. Physik 1933, 87, 238
Michaelis, L.; Schubert, M.P.; Granick, S. J. Am. Chem. Soc. 1939, 61, 1981
Ar

Ar
N

Ar

Ar

1/2 X2

N

N
Ar

.

Ar

X-

N+

Ar

Ar

.

Wieland, H. Chem. Ber. 1907, 40, 4260; 4263
Ar3 N + 1/2 Br2

Ar3 N+ Br-

Wieland, H.; Wecker, E. Chem. Ber. 1910, 43, 699
SbF 5

.
+

.
+

SbF 5

228
Meyer, K.H. Chem. Ber. 1910, 43, 161
Hilpert, S.; Wolf, L. Chem. Ber. 1913, 46, 2215
NH

.
+

NH

-

-e
S

NH

-

-e

S

S

Kehrmann, F.; Speitel, J.; Grandmougin, E. Chem. Ber. 1914, 47, 2976
Kehrmann, F.; Diserens, L. Chem. Ber. 1915, 48, 318
Weitz, E.Z. Z. Elektrochem. 1928, 34, 538
Weitz, E.; Meitzner, E. Chem. Ber. 1931, 64B, 2909
Giusa, R. Gazz. Chim. Ital. 1945, 75, 162
Hughes, G.K.; Hush, N.S. J. Proc. Roy. Soc. New South Wales 1947, 81, 48
Holden, A.N.; Yager, W.A.; Merritt, F.R. J. Chem. Phys. 1951, 19, 1319

.
+

H2 SO4

O

O

N

O

N

O

O

O

H2 SO4
N

O

N

O

Hirschon, G.M.; Gardner, D.M.; Fraenkel, G.K. J. Am. Chem. Soc. 1953, 75, 4115
Hoijtink, G.J.; Weijland, W.P. Rec. Trav. Chim. Pays-Bas 1957, 76, 836
Kon, H.; Blois, M.S. J. Chem. Phys. 1958, 28, 743

.
+

+2

229

SbF 5

Ar-NH2

.
+

ArNH2

Kainer, H.; Hausser, K.H. Chem. Ber. 1957, 86, 1563
Lewis, I.C.; Singer, L.S. J. Chem. Phys. 1965, 43, 2712
Lewis, I.C.; Singer, L.S. J. Chem. Phys. 1966, 44, 2082
- eR2 N

CH

CH

CH

CH

R2 N

NR2

CH

CH

CH

CH

.

S
CH CH

.

N+

.

N+

CH CH CH CH
N+

NR2

n

n
S

.
+

N

Hünig, S. Ann. Chem. 1964, 676, 32
Hünig, S.; Balli, H.; Conrad, H.; Schott, A. Ann. Chem. 1964, 676, 36; 52
Hünig, S. Chem. Eng. News 1966, 44, 102
Hünig, S.; Geiger, H.; Kaupp, G.; Kniese, W. Ann. Chem. 1966, 697, 116

- e-

+
R2 N

+
CH

CH

CH

CH

NR2

n

230
R1

R1

.


N

Cl

H2 SO4

R2

N+

H

R2

Danen, W.C.; Rickard, R.C. J. Am. Chem. Soc. 1972, 94, 3254
O

.
_

O

O

.



+
Ph

Ph
CN

.

Ph

Ph

B+

A-

Ph

+

A

.

+
Ph

.

.

Ph

Ph

O+

+ ROH

Ph
Ph

.

R
Ph

Ph

-.

Ph

+ A

Ph

H

+
Ph

+
Ph

CN

+
Ph

.
+

CN

A-

Ph

_

+

Ph

.

.

A-

Ph

.

O

Ph

Neutefel, R.A.; Arnold, D.R. J. Am. Chem. Soc. 1973, 95, 4080
Pincock, J.A. Can. J. Chem. 2003, 81, 413

.

R
Ph

+ A

.

B+

.

231

N

N

X

X = CR 3 , NR2 , OMe, Cl, NMe3 +

X

- e-

Nelsen, S.F.; Kessel, C.R.; Brien, D.J. J. Am. Chem. Soc. 1980, 102, 702

ROOC

ROOC

ROOC

N

.
.
N

N

N

COOR

+ Ph 3 P

.
.

ROOC

N

_
N

COOR

+ Ph 3 P

ROOC

N

+

COOR

N

N

ROOC

N

.
N

N

COOR

.

+ Ph 3 P+

COOR

+

_

ROOC

N

+ Ph 3 P
PPh3

+

COOR

+

N

N

+
COOR
N
PPh3

COOR
N

.

ROOC

+

_

ROOC

N

N

N

PPh3

+

N

+

N

PPh3
ROOC

ROOC

PPh3

PPh3

ROOC

+ Ph 3 P+

COOR

_

COOR

COOR
N

.

_

COOR

.

+

+ Ph 3 P+

N
PPh3

+

Camp, D.; Hanson, G.R.; Jenkins, I.D. J. Org. Chem. 1995, 60, 2977

ROOC

.
N

_
N

COOR

232

.

Br

H+


O
MeO

- Br

.

.
+

OH

O
MeO

MeO

Schepp, N.P. J. Org. Chem. 2004, 69, 4931
Distonic radical cations
Reviews:
Radom, L.; Bouma, W.J.; Nobes, R.H. Pure Appl. Chem. 1984, 56, 1831
Yates, B.F.; Bouma, W.J.; Radom, L. Tetrahedron 1986, 42, 6225
Westwood, N.P.C. J. Molecular Struct. 1988, 173, 227
Bouchoux, G. Mass Spectrometry Rev. 1988, 7, 1
Hammerum, S. Mass Spectrometry Rev. 1988, 7, 123
Bouchoux, G. Mass Spectrometry Rev. 1988, 7, 203
Stirk, K.M.; Kiminikenen, L.K.M.; Kenttaemaa, H.I. Chem. Rev. 1992, 92, 1649
Bouchoux, G. Trends in Org. Chem. 1993, 4, 161
Kenttaemaa, H.I. Org. Mass Spectrometry 1994, 29, 1
Smith, R.L.; Chou, P.K.; Kenttaemaa, H. in Structure, Energetics, and Dynamics of Organic Ions, (T. Baer, C.Y. Ng, I. Powis, eds.) Wiley:
Chichester, 1996, p. 197
Audier, H.E.; Fossey, J.; Leblanc, D.; Mourgues, P.; Troude, V. NATO ASI Ser., Ser. C 1999, 521, 27
Gebecki, J.; Marcinek, A. in General Aspects of the Chemistry of Radicals, (Z.B. Alfassi, ed.) Wiley: Chichester, 1999, p. 175
Golding, B.T.; Radom, L. J. Am. Chem. Soc. 1976, 98, 6331 (prediction of stability in gas phase)
Bouma, W.J.; MacLeod, J.K.; Radom, L. Nouv. J. Chim. 1978, 2, 439

233

.

+

CH2

X = OH, NH2 , SH, Cl, Br

XH

H

.

H

.

Cl+

H

+

CH2

O

Cl

CH3

Holmes, J.L.; Lossing, F.P.; Terlouw, J.K.; Burgers, P.C. J. Am. Chem. Soc. 1982, 104, 2931
Terlouw, J.K.; Heerma, W.; Dijkstra, G.; Holmes, J.L.; Burgers, P.C. Int. J. Mass Spectrom. Ion Phys. 1983, 47, 147
_

+

CH2

OH2

.

+

CH2

OH2

+ e-

Yates, B.F.; Bouma, W.J.; Radom, L. J. Am. Chem. Soc. 1984, 106, 5805

.
+

+ NH 3

+

.

NH3

.

CH2

+
NH3

+ CH 2 =CH 2

Sack, T.M.; Cerny, R.L.; Gross, M.L. J. Am. Chem. Soc. 1985, 107, 4562

.

CH2 -Z-CH2 -X-H +

.

CH3 -Z-CH2 -X +

Z = bond, CH2 , CHMe, CH2 CH2 ; X = OH, NH2
Wesdemiotis, C.; Danis, P.O.; Feng, R.; Tso, J.; McLafferty, F.W. J. Am. Chem. Soc. 1985, 107, 8059

234



Ar

acetone-d6

+

Ar

.

+

.

Ar

Ar

Ar

Ar
O

O
Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl
O

O

Ar
Ar

Ar

Cl
Cl

Ar

O

Cl

Cl
O

O

Cl

Cl

Cl

O
Cl

Miyashi, T.; Takahashi, Y.; Mukai, T.; Roth, H.D.; Schilling, M.L.M. J. Am. Chem. Soc. 1985, 107, 1079

.

+
OH2

Postma, R.; Ruttink, P.J.A.; Van Baar, B.; Terlouw, J.K.; Holmes, J.L.; Burgers, P.C. Chem. Phys. Lett. 1986, 123, 409

235

.
+

+

.

NH2

NH2

Qin, X.Z.; Williams, F. J. Am. Chem. Soc. 1987, 109, 5957

.
+

O

O

+

.

- eO2N

O

- CH3
O2N

O2N

Moraes, L.A.B.; Eberlin, M.N. J. Am. Chem. Soc. 1998, 120, 11136

:

Silylenes and germylenes
Si
R1

R2

Reviews:
Denk, M.; West, R.; Hayashi, R. in Organosilicon Chemistry II: from molecules to materials, (N. Auner; J. Weis, eds.) VCH: Weinheim,
1994, p. 251
Weidenbruch, M. Coord. Chem. Rev. 1994, 130, 275
Becerra, R.; Walsh, R. Res. Chem. Intermediates 1995, 3, 263
Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1
West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785
Gehrhus, B.; Lappert, M.F. Phosphorus, Sulfur, Silicon and Related Elements 1997, 124-125, 537
Gaspar, P.P.; West, R. in The Chemistry of Silicon Compounds, (Z. Rappoport; Y. Apeloig, eds.) Wiley: Chichester, 1998, Vol. 2 (Pt. 3), p. 2463

236
Kira, M. Pure Appl. Chem. 2000, 72, 2333
Veszpremi, T. Adv. Molecular Structure Res. 2000, 6, 267
Haaf, M.; Schmedake, T.A.; West, R. Acc. Chem. Res. 2000, 33, 704
Tokitoh, N.; Okazaki, R. Coord. Chem. Rev. 2000, 210, 251 (silylenes, germylenes, stannylenes, plumbylenes)
Gehrhus, B.; Lappert, M.F. J. Organometallic Chem. 2001, 617-618, 209 (stable bis(amino)silylenes)
Gaspar, P.P.; Xiao, M.; Pae, D.H.; Berger, D.J.; Haile, T.; Chen, T.; Lei, D.; Winchester, W.R.; Jiang, P. J. Organometallic Chem. 2002, 646, 68

:

Gaspar, P.P.; Pate, B.D.; Eckelman, W. J. Am. Chem. Soc. 1966, 88, 3878
Atwell, W.H.; Weyenberg, D.R. J. Am. Chem. Soc. 1968, 90, 3438
Atwell, W.H.; Weyenberg, D.R. Angew. Chem. Int. Ed. Engl. 1969, 8, 469
Atwell, W.H.; Mahone, L.G.; Hayes, S.F.; Uhlmann, J.G. J. Organometal. Chem. 1969, 18, 69
Gaspar, P.P.; Hwang, R.J. J. Am. Chem. Soc. 1974, 96, 6198
Henis, J.M.S.; Stewart, G.W.; Gaspar, P.P. J. Chem. Phys. 1974, 61, 4860
Hwang, R.J.; Gaspar, P.P. J. Am. Chem. Soc. 1978, 100, 6626
Gaspar, P.P. React. Intermed. 1978, 1, 229
Ge
R1

R2

Reviews:
Lappert, M.F.; Rowe, R.S. Coordin. Chem. Rev. 1990, 100, 267 (germylenes, stannylenes, plumbylenes)
Neumann, W.P. Chem. Rev. 1991, 91, 311 (germylenes and stannylenes)
Neumann, W.P.; Weisbeck, M.P.; Wienken, S. Main Group Metal Chem. 1994, 17, 151
Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1
Tokitoh, N.; Okazaki, R. Coord. Chem. Rev. 2000, 210, 251 (silylenes, germylenes, stannylenes, plumbylenes)
950 C
CaH2 + Ge

CaGe
- H2

2 H2 O
- Ca(OH)2

GeH2

Royen, P.; Schwarz, R. Z. Anorg. Allgem. Chem. 1933, 211, 412 (first claim, later refuted)

237

:

H

_

Na+ + Ph

Ge
H

NaBr + Ph

Br

H

H

+

Ge
H

H

Glarum, S.N.; Kraus, C.A. J. Am. Chem. Soc. 1950, 72, 5398
Silylium ions (silylenium ions, silicenium ions, silyl cations, silicocations)
R1
Si+
R2

R3

Reviews:
Lambert, J.B.; Kania, L.; Zhang, S. Chem. Rev. 1995, 95, 1191
Corriu, R.J.P.; Henner, M. J. Organometallic Chem. 1974, 74, 1
Reed, C.A. Acc. Chem. Res. 1998, 31, 325
(iPr)3 SiH + Ph 3 C+ [CB11 H6 X6 ]-

Ph3 CH + (iPr) 3 Si+ [CB11 H6 X6 ]-

X = Cl, I
Xie, Z.; Manning, J.; Reed, R.W.; Mathur, R.; Boyd, P.D.W.; Benesi, A.; Reed, C.A. J. Am. Chem. Soc. 1996, 118, 2922
Reed, C.A.; Xie, Z.; Bau, R.; Benesi, A. Science 1993, 262, 402
Ph3 C+ X- + R3 SiH

Ph3 CH + R 3 Si+ X-

Me(iPr)2 Si+ XEt3 Si+ X(Me3 Si)3 Si+ X-

X = [B(F 5 Ph)4 ]

238
Lambert, J.B.; Zhang, S.; Ciro, S.M. Organometallics 1994, 13, 2430
R3 Si+ [Br6 -CB11 H6 ]-

R = Et, iPr, tBu

(tBu)2 MeSi+ [Br6 -CB11 H6 ]Xie, Z.; Bau, R.; Benesi, A.; Reed, C.A. Organometallics 1995, 14, 3933
R

Mes
R

Mes
Si

+

+ R3 Si [B(F5 Ph)4 ]

Mes

-

+

Si

-

Mes3 Si [B(F5 Ph)4 ] +

R

R = Ph, Et
Lambert, J.B.; Zhao, Y. Angew. Chem. Int. Ed. 1997, 36, 400
Mes

Et

Mes

Et

Si

+

+ Et3 Si [HCB11 Me5 Br6 ]

Mes

-

+

-

Si

Mes3 Si [HCB11 Me5 Br6 ] +
Et

Kim, K.C.; Reed, C.A.; Elliott, D.W.; Mueller, L.J.; Tham, F.; Lin, L.; Lambert, J.B. Science 2002, 297, 825
OH
R1

H+

Me3Si
Si
SiMe3

SiMe3
R1

R1

Me3Si

R2

- H2 O

Me3Si

+
Si
Me3Si
SiMe3

+

R2

Si
Me3Si
SiMe3

Sternberg, K.; Michalik, M.; Oehme, H. J. Organometallic Chem. 1997, 533, 265

R2

SiMe3
R1

MeOH MeO
- H+

Si
Me3Si
SiMe3

R2

239
Tetrahedral Intermediates
Reviews:
Jencks, W.P. Prog. Phys. Org. Chem. 1964, 2, 63
Johnson, S.L. Adv. Phys. Org. Chem. 1967, 5, 237
Jencks, W.P. Catalysis in Chemistry and Enzymology, McGraw-Hill: New York, 1969
Jencks, W.P. Chem. Rev. 1972, 72, 705
Barnett, R.E. Acc. Chem. Res. 1973, 6, 41
Capon, B.; Ghosh, A.K.; Grieve, D.M.A. Acc. Chem. Res. 1981, 14, 306
McClelland, R.A.; Santry, L.J. Acc. Chem. Res. 1983, 16, 394
Capon, B.; Dosunmu, M.I.; De Nazare, M.; Sanchez, M. Adv. Phys. Org. Chem. 1985, 21, 37
Bowden, K. Adv. Phys. Org. Chem. 1993, 28, 171
Perrin, C.L. Acc. Chem. Res. 2002, 35, 28
O-

O
C
R1

+ Nu

R1

C

R2

R2
Nu +
O-

O
S
R1

+ Nu

R1

S

R2

R2
Nu +
O-

O
P
R1

+ Nu

R1

P

R2
Nu +

R2

240

H

Ph
N

Ph
N

HBr

NHPh

O

H2 O
R

OH

+ EtOH

- HBr
R

R

OEt

OEt

R

OEt

NHPh

Br

Stieglitz, J. Am. Chem. J. 1899, 21, 101
O

O - Na+

+ NaOEt
CF3

CF3

OEt

OEt
OEt

Swarts, F. Bull. Soc. Chim. Belg. 1926, 35, 414
Helferich, B.; Muller, A. Chem. Ber. 1930, 63B, 2142
Bender, M.L. J. Am. Chem. Soc. 1951, 73, 1626
Bender, M.L. J. Am. Chem. Soc. 1953, 75, 5986
Zaugg, H.E.; DeNet, R.W.; Michaels, R.J. Jr. J. Org. Chem. 1961, 26, 4828
Cordes, E.H.; Childers, M. J. Org. Chem. 1964, 29, 968
Bender, M.L.; Kezdy, F.J. J. Am. Chem. Soc. 1964, 86, 3704
Martin, R.B.; Hedrick, R.I.; Parcell, A. J. Org. Chem. 1964, 29, 3197
Jencks, W.P.; Gilchrist, M. J. Am. Chem. Soc. 1964, 86, 5616
Fedor, L.R.; Bruice, T.C. J. Am. Chem. Soc. 1964, 86, 5697
Kirby, A.J.; Jencks, W.P. J. Am. Chem. Soc. 1965, 87, 3217
Fedor, L.R.; Bruice, T.C. J. Am. Chem. Soc. 1965, 87, 4138
Caplow, M. J. Am. Chem. Soc. 1965, 87, 5774
Biffin, M.E.C.; Crombie, L.; Elvidge, J.A. J. Chem. Soc. 1965, 7500
OH

+

O

-O

+ NH 2 OH

NH2 OH

HO

NHOH

HA
- H2 O

N

241

Reimann, J.E.; Jencks, W.P. J. Am. Chem. Soc. 1966, 88, 3973
DeJersey, J.; Zerner, B. Biochem. Biophys. Res. Commun. 1967, 28, 173
Robinson, D.R.; Jencks, W.P. J. Am. Chem. Soc. 1967, 89, 7098
Robinson, D.R.; Jencks, W.P. J. Am. Chem. Soc. 1967, 89, 7088
Thiirenium Ions
R1
S+

R2

R3

Reviews:
Pasquato, L.; Destro, R.; Lucchini, V.; Modena, G. Phosphorus, Sulfur, and Silicon and the related elements 1999, 153-154, 235
Lucchini, V.; Modena, G.; Pasquato, L. Gazz. Chim. Ital. 1997, 127, 177
Modena, G.; Pasquato, L.; Lucchini, V. Phosphorus, Sulfur, and Silicon and the related elements 1994, 95-96, 265
Capozzi, G.; Lucchini, V.; Modena, G. Rev. Chem. Intermediates 1979, 2, 347
C* = 14 C
Ph
Ph

OSO2 C6H 4p-Br
C*

BF3

C

C*

pBrC6 H4 SO3

Ph
C6 H4X

Ph

C*

C
S+

XC6H 4S

Ph

Ph
-

C*

Ph

- pBrC6 H4 SO3 H

X

S

X

S

Ph

242
Ph

H2
Raney Ni

Ph

C*H
CH2

Ph

NBS

CH
C*H2

Ph

X

C*

X

Ph

Ph

C*

C
O

+ PhCOOH

X

+

O

+ PhC * OOH

X

Capozzi, G.; Melloni, G.; Modena, G.; Tonellato, U. Chem. Commun. 1969, 1520
Modena, G.; Tonellato, U. J. Chem. Soc. B 1971, 381 (stereochemical evidence)
Modena, G.; Tonellato, U. J. Chem. Soc. B 1971, 374 (kinetic evidence)
Burighel, A.; Modena, G.; Tonellato, U. Chem. Commun. 1971, 1325
HS
C+
H

H
H

65.9 kcal/mol

S+

H

H

Denes, A.S.; Csizmadia, I.G.; Modena, G. Chem. Commun. 1972, 8

KMnO4

C
CH

Ph

X

Ph

C*H

Ph
X

Ph

243

R1

R1

Cl

R3 -S

R2

R2

Cl

R3 -S

R1

O3SAr
R3

R3 -S

R2

R2

O3SAr

S+

HCl
- ArSO3 H
R1

R3 -S

Cl-

R2

R1

R1

R2

+ R3 -SCl

Modena, G.; Scorrano, G.; Tonellato, U. J. Chem. Soc. Perkin Trans. 2 1973, 493
Transition Metal Carbene Complexes
R1
[Ln]M
R2

Reviews:
Fischer, E.O. in Advances in Organometallic Chemistry, (F.G.A. Stone, R. West, eds.), Academic Press: Orlando, FL, 1976; Vol. 14, p. 1 - 32
(carbene and carbyne complexes)
Schrock, R.R. Acc. Chem. Res. 1979, 12, 98
Dötz, K.H.; Fischer, H.; Hofmann, P.; Kreissl, F.R.; Schubert, U.; Weiss, K. Transition Metal Carbene Complexes, Verlag Chemie: Weinheim,
1983
Dötz, K.H. Angew. Chem. Int. Ed. 1984, 23, 587
Roper, W.R. NATO ASI Series, Ser. C. 1989, 269, 27
Harvey, D.F.; Sigano, D.M. Chem. Rev. 1996, 96, 271

244
de Meijere, A. Pure Appl. Chem. 1996, 68, 61
Barluenga, J. Pure Appl. Chem. 1996, 68, 543
Hegedus, L.S. Tetrahedron 1997, 53, 4105
Aumann, R.; Nienhaber, H. Adv. Organometallic Chem. 1997, 41, 163
Barluenga, J. Pure Appl. Chem. 1999, 71, 1385
Herndon, J.W. Tetrahedron 2000, 56, 1257
de Meijere, A.; Schirmer, H.; Duetsch, M. Angew. Chem. Int. Ed. 2000, 39, 3964
Barluenga, J.; Fananas, F.J. Tetrahedron 2000, 56, 4597
Sierra, M.A. Chem. Rev. 2000, 100, 3591
Bernasconi, C.F. Adv. Phys. Org. Chem. 2002, 37, 137
Fischer carbene
CO
OC
OC

M

CO
CO

PhLi / Et2 O

CO

OC

CO

M

OC
CO

O-

Li+

C

OC

CO

OC

Ph

Me3 O+ BF4 -

O-

C

CO

CO OMe

CO

CH2 N2

M
CO

OC
Ph

- N2

Fischer, E.O.; Maasbol, A. Angew. Chem. Int. Engl. Ed. 1964, 3, 580
Fischer, E.O.; Maasbol, A. Angew. Chem. 1964, 76, 645
Aumann, R.; Fischer, E.O. Angew. Chem. Int. Ed. 1967, 6, 879
Fischer, E.O. Adv. Organomet. Chem. 1976, 14, 1

OC

Ph

CO

- Me4 N+ X-

M = W, Cr, Mo

OC

M

CO

- LiCl

- LiBF4
- Me2 O

OC

CO

Me4 N+ Cl-

HX

CO

OH

M
CO

Ph

Me4 N+

245
O - K+

C8 K

R1 -COCl

K2 [M(CO)5 ]

M(CO)6

(OC) 5M

O

R1

R2 -X

R3
R1

N

OR2

R4

K+
_

O - K+

(OC) 5M

(OC) 5M

R3
N

R1
R4

R1

Me3 SiCl
R3
N

R4

(OC) 5M
R1

Semmelhack, M.F.; Lee, G.R. Organometallics 1987, 6, 1839
Imwinkelried, R.; Hegedus, L.S. Organometallics 1988, 7, 702
Schrock carbene

246
2 MCl5 + 3 Zn[CH2 CMe3 ]2

2 M[CH2 CMe3 ]3 Cl2
- 3 ZnCl2

M[CH2 CMe3 ]3 Cl2 + 2 LiCH2 CMe3

Me3CCH 2

- 2 LiCl
- CMe4

Me3CCH 2

H

M

Me3CCH 2

CMe3

M = Ta, Nb
Schrock, R.R.; Meakin, P. J. Am. Chem. Soc. 1974, 96, 5288
Schrock, R.R. J. Am. Chem. Soc. 1974, 96, 6796
Schrock, R.R.; Fellmann, J.D. J. Am. Chem. Soc. 1978, 100, 3359
Schrock, R.R. J. Organometallic Chem. 1976, 122, 209
Cp
CH3

H

Ta
H

Cp

Schrock, R.R. J. Am. Chem. Soc. 1975, 97, 6577
Schrock, R.R.; Guggenberger, L.J. J. Am. Chem. Soc. 1975, 97, 6578
Transition Metal Carbyne Complexes
[Ln]M

C

R

Reviews:
Fischer, E.O. in Advances in Organometallic Chemistry, (F.G.A. Stone, R. West, eds.), Academic Press: Orlando, FL, 1976; Vol. 14, p. 1 - 32
(carbene and carbyne complexes)

247
CO
OC
OC

CO

CO Ph

+ BI3

W

I
OC

OMe

CO

W

CO
C

Ph

+ CO + BI2 OMe

CO

Fischer, E.O.; Kreis, G.; Kreiter, C.G..; Cornelius, G.; Müller, J.; Huttner, G.; Lorenz, H. Angew. Chem. 1973, 85, 618
Fischer, E.O.; Kreiter, C.G.; Müller, J.; Huttner, G.; Lorenz, H. Angew. Chem. Int. Ed. 1973, 12, 564
Fischer, E.O.; Kreis, G.; Kreissl, F.; Kalbfus, W.; Winkler, E. J. Organometallic Chem. 1974, 65, C53
Transition Metal Ketenyl Complexes
O

[M]

R1

R2

Reviews:
Geoffrey, G.L.; Bassner, S.L. Adv. Organometallic Chem. 1988, 28, 1 (ketenyl complexes, heterovinylidene complexes)
Gibson, S.E.; Peplow, M.A. Adv. Organometallic Chem. 1999, 44, 275 (vinylketenyl complexes)
Kirmse, W. Eur. J. Org. Chem. 2002, 2193
Singh, G.S.; Mdee, L.K. Curr. Org. Chem. 2003, 7, 1821

248

2 PMe3
OC

W

CO

Me3P
OC

W

PMe 3
O

C

Kreissl, F.R.; Frank, A.; Schubert, U.; Lindner, T.L.; Hutner, G. Angew. Chem. 1976, 88, 649
Kreissl, F.R.; Eberl, K.; Uedelhoven, W. Chem. Ber. 1977, 110, 3782
Kreissl, F.R.; Uedelhoven, W.; Eberl, K. Angew. Chem. 1978, 90, 908
Uedelhoven, W.; Eberl, K.; Kreissl, F.R. Chem. Ber. 1979, 112, 3376
Eberl, K.; Uedelhoven, W.; Karsch, H.H.; Kreissl, F.R. Chem. Ber. 1980, 113, 3377
_

1. 2 KCN
(- KBr)
N

CO
W

N

CO

C
Br

2. [Ph3 P-N=PPh3 ]+ XPh ( - KX)

N
NC
N

CN

Ph

[Ph3 P-N=PPh3 ]+

W
CO

O

Fischer, E.O.; Filippou, A.C.; Alt, H.G.; Ackermann, K. J. Organometallic Chem. 1983, 254, C21 (first anionic ketenyl transition metal complex)

249
OMe

Cl

HCl

AgPF6

(Cp)(CO)2 Fe

(Cp)(CO)2 Fe

(Cp)(CO)2 Fe

- AgCl

- MeOH
- MeOH

+

HBF 4
+

BF4 -

CH2

Fe(CO)2 (Cp)
CH2

C

O

Bodnar, T.W.; Cutler, A.R. J. Am. Chem. Soc. 1983, 105, 5926
Transition Metal Keteniminium Complexes
R3

R3

R

R3

N+

N+
[M]-

[M]-

R1

R2

R1

R2

Reviews:
Aumann, R. Angew. Chem. 1988, 100, 1512
PPh3
CO
Ir

PPh3

+

K

+

N

PPh3

CN

_
Ph3 P

Ir
OC

C

- KCl
Cl

PF 4 -

CO

+
(Cp)(CO)2 Fe

CH2

CN

CN
N

C
CN

PF 4 -

250

Lenarda, M.; Baddley, W.H. J. Organometallic Chem. 1972, 39, 217
Marchand-Brynaert, J.; Ghosez, L. J. Am. Chem. Soc. 1972, 94, 2869; 2870
NMe2

NMe2

+ Na[Re(CO)5 ]

N+

- NaCl
Re(CO)5

Cl

NMe2

NMe2

+ Na[Fe(CO)2 (Cp)]

N+

- NaCl

Cl

_

NMe2

Co(CO)3

+ Na[Co(CO)4 ]

N+

Fe(CO)2 (Cp)

N+

- NaCl

- CO

Cl

_
Mo(CO) 2(Cp)

NMe2

+ Na[Mo(CO)3 (Cp)]

N+

- NaCl

Cl

King, R.B.; Hodges, K.C. J. Am. Chem. Soc. 1974, 96, 1263

N+

- CO

251
CH3

(OC)5 Cr[Cy-N=C=C(Me)(OMe)]

+ Cy-NC

(CO) 5Cr

Cr(CO)5 + Cy-N=C=C(Me)(OMe)

OCH3

Kreiter, C.G.; Aumann, R. Chem. Ber. 1978, 111, 1223
Ph
OEt
(CO) 5W

+ Cy-NC

Ph

OEt

R-N=C=O (CO)5W

R
N

W(CO)5 [Cy-N=C=C(OEt)(Ph)]
Cy

KMnO4 O

R
N

Fe(NO3 )3

N

Ph

OEt

N
Cy

O

O

Aumann, R.; Kuckert, E. Chem. Ber. 1986, 119, 156
Cp2 V + R2 C=C=N-R 1

Cp2 V[R2 C=C=N-R 1 ]

Sielisch, T.; Behrens, U. J. Organometallic Chem. 1986, 310, 179
H
Ph
(CO) 5W

(CO) 5W

+ Cy-NC
OEt

OEt
R
N

Cy

C
Ph

Transition Metal Iminium Complexes

Ph
H

OEt
H

(CO) 5W

(CO) 5W
N
Cy

Aumann, R.; Kuckert, E. Chem. Ber. 1987, 120, 1939

EtO

R

Ph

N
Cy

R

252
R1

R3
N+

R2

M[Ln] R
4

Reviews:
None.
+
HCl

N
OC
P
Ph

Ph

W

NH

Cl-

PPh2
CO

CO

OC
P
Ph

Ph

W
CO

PPh2
CO

HCl
NH
PPh2
Cl
Cl

PPh2
W
CO
CO

Ainscough, E.W.; Brodie, A.M.; Burrell, A.K.; Kennedy, S.M.F. J. Am. Chem. Soc. 2001, 123, 10391
Transition Metal Silene Complexes
R
[Ln]M

Si
R

Reviews:
Lickliss, P.D. Chem. Soc. Rev. 1992, 21, 271
Ogino, H. The Chemical Record 2002, 2, 291

253
NEt 2

CH3


Fe(CO)5 + H

Si

(CO) 4Fe

CH3

NHEt2

Si

- CO
CH3

CH3

Schmid, G.; Welz, E. Angew. Chem. Int. Ed. 1977, 16, 785
Cl

Na2 Fe(CO)4 + tBuO

O

Si

Cl

+ (CH3) 2N

P

(CO) 4Fe

N(CH3) 2

- 2 NaCl
OtBu

O

OtBu
N

Si
OtBu

N(CH3) 2

P

N(CH3) 2

N(CH3) 2

Zybill, C.; Muller, G. Angew. Chem. Int. Ed. 1987, 26, 669

PMe 3 Ph

_

Ru+

PMe 3

CH3 CN
Si

OTf

+ NaBPh 4

_

Ph

Ru+2 Si

NCCH 3

- NaOTf
PMe 3 Ph

PMe 3

Straus, D.A.; Tilley, T.D.; Rheingold, A.L.; Geib, S.J. J. Am. Chem. Soc. 1987, 109, 5872

Ph

BPh4 -

254

S
(CO) 4Os

PCy3

Si
Ru+

Pt

H

+

SEt

BPh4 -

Si

_
SEt

PCy3

Cy = cyclohexyl
Grumbine, S.D.; Tilley, T.D.; Rheingold, A.L. J. Am. Chem. Soc. 1993, 115, 358
Grumbine, S.D.; Tilley, T.D.; Arnold, E.P.; Rheingold, A.L. J. Am. Chem. Soc. 1993, 115, 7884
Grumbine, S.D.; Tilley, T.D.; Arnold, E.P.; Rheingold, A.L. J. Am. Chem. Soc. 1994, 116, 5495
NMe2

NMe2


Fe(CO)5 + H

Si

(CO) 4Fe

NMe2

NHMe2

Si

- CO
NMe2

NMe2

Bodensieck, U.; Braunstein, P.; Deck, W.; Faure, T.; Knorr, M.; Stern, C. Angew. Chem. Int. Ed. 1994, 33, 2440
Transition metal vinyl cation complexes
R1

M[Ln]

[Ln]M

+

+

[Ln]M

+
R2

R2

R1

R1

Reviews:
Chisholm, M.H.; Clark, H.C. Acc. Chem. Res. 1973, 6, 202

R2

255

R
Cl

+

R

Q

+

Pt
Q

+ AgPF6

Me

[PF 6 -]

Q

- AgCl

Pt
R

Q

Me

R

R

R

Q

+
Q

+

R

Pt
Q

Me

Q
R

R

+
Me

Pt
Q

Me

Pt
Q

Clark, H.C.; Puddephatt, R.J. Chem. Commun. 1970, 92
Clark, H.C.; Puddephatt, R.J. Inorg. Chem. 1970, 9, 2670
Clark, H.C.; Ruddick, J.D. Inorg. Chem. 1970, 9, 1226
Chisholm, M.H.; Clark, H.C. Chem. Commun. 1970, 763
Clark, H.C.; Puddephatt, R.J. Inorg. Chem. 1971, 10, 18
Chisholm, M.H.; Clark, H.C. Inorg. Chem. 1971, 10, 1711; 2557
Chisholm, M.H.; Clark, H.C. J. Am. Chem. Soc. 1972, 94, 1532
Transition Metal Vinylidene Complexes

R

256
R1
[Ln]M

C

C
R2

Reviews:
King, R.B. Acc. Chem. Res. 1970, 3, 417
Herrmann, W.A. Adv. Organometallic Chem. 1982, 20, 159
Bruce, M.I.; Swincer, A.G. Adv. Organometallic Chem. 1983, 22, 59
Sailor, M.L.; Shriver, D.F. Acc. Chem. Res. 1988, 21, 374 (heterovinylidene complexes)
Bruce, M.I. Chem. Rev. 1991, 91, 197
Bruce, M.I. Chem. Rev. 1998, 98, 2797
Puerta, M.C.; Valegra, P. Coord. Chem. Rev. 1999, 193-195, 977
Lin, Y.C. J. Organometallic Chem. 2001, 617-618, 141 (Ru)
Bruneau, C. Topics Organometallic Chem. 2004, 11, 125 (Ru, Os)
King, R.B. Coord. Chem. Rev. 2004, 248, 1533
Selegue, J.P. Coord. Chem. Rev. 2004, 248, 1543
Watatsuki, Y. J. Organometallic Chem. 2004, 689, 4092
Ph2 C=C=O

+ Fe2 (CO)9

Fe2 (µ-C=CPh 2 )(CO)8 + CO2

Mills, O.S.; Redhouse, A.D. Chem. Commun. 1966, 444
Mills, O.S.; Redhouse. A.D. J. Chem. Soc. A 1968, 1282
NC

Cp

Cl

+ 2 PR 3
NC

M(CO)3Cp

R3 P
Cl

M

CN

+ 3 CO

C

PR3

CN

M = W, Mo; R = PPh3 , P(OMe)3 , P(OPh) 3 , P(OEt)3 , AsPh 3 , SbPh3
King, R.B.; Saran, M.S. Chem. Commun. 1972, 1053

257
(CO) 5M

M(CO)5 Cl

+ Cl-

CN

X

CN

CN

X

CN

(CO) 3(Cp)M

CN

M(Cp)(CO)3 -

+ ClX

CN

X = H, Cl, CN; M = Mo, W
King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1972, 94, 1784
King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1973, 95, 1811
King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1973, 95, 1817
Transition Metal Vinylidenecarbene (allenylidene) Complexes
R1
[Ln]M

C

C

C
R2

Reviews:
Bruce, M.I.; Swincer, A.G. Adv. Organometallic Chem. 1983, 22, 59
Bruce, M.I. Chem. Rev. 1991, 91, 197
Werner, H. J. Organometallic Chem. 1994, 475, 45
Werner, H. Chem. Commun. 1997, 903
Bruce, M.I. Coord. Chem. Rev. 1997, 166, 91
Cadiero, V.; Gamasa, M.P.; Gimeno, J. Eur. J. Inorg. Chem. 2001, 571
Werner, H.; Ilg, K.; Lass, R.; Wolf, J. J. Organometallic Chem. 2002, 661, 137
Winter, R.F.; Zalis, S. Coord. Chem. Rev. 2004, 248, 1565
Rigaut, S.; Touchard, D.; Dixneuf, P.H. Coord. Chem. Rev. 2004, 248, 1585

258
M(CO)5 [=C(OEt)CH=C(Ph)(NEt2 )] + EX3
M = Cr, W

M(CO)5 [=C=C=C(Ph)(NEt 2 )] + [EtOEX3 ]- H+

EX3 = BF 3 (when M = Cr), AlEt3 (when M = W)

Berke, H. Angew. Chem. Int. Ed. Engl. 1976, 15, 624
Fischer, E.O.; Kalder, H.J.; Frank, A.; Köhler, F.H.; Huttner, G. Angew. Chem. Int. Ed. 1976, 15, 623
[Ru(=C=C=CPh2 )(PMe3 )2 Cp]+
Selengue, J.P. Organometallics 1982, 1, 217
Triplet Ketones (excited state)
*3

O

R1

R2

Reviews:
Brand, J.C.D.; Williamson, D.G. Adv. Phys. Org. Chem. 1963, 1, 365
Yang, N.C. Reactivity of the Photoexcited Organic Molecule, Proc. Conf. Chem. 1965, 145
Parker, C.A. Ber. Bunsen-Gesell. 1969, 73, 764
Stephenson, L.M.; Hammond, G.S. Angew. Chem. Int. Ed. 1969, 8, 261
Davidson, R.S. Organic Reaction Mechanisms 1971, 467
Ireland, J.F.; Wyatt, P.A.H. Adv. Phys. Org. Chem. 1976, 12, 132
Davidson, R.S. Adv. Phys. Org. Chem. 1983, 19, 1
Pedulli, G.F. Rev. Chem. Intermediates 1986, 7, 155
Chan, I.Y. Rev. Chem. Intermediates 1987, 8, 339
Wan, J.K.S.; Depew, M.C. Res. Chem. Intermediates 1992, 18, 227
Armesto, D.; Ortiz, M.J.; Agarrabeitia, A.R. in CRC Handbook of Organic Photochemistry and Photobiology, 2nd ed., (W. Horspool; F. Lenci,
eds.) CRC Press: Boca Raton, FL, 2004, p. 77/1
Wagner, P.J.; Klan, P. in CRC Handbook of Organic Photochemistry and Photobiology, 2nd ed., (W. Horspool; F. Lenci, eds.) CRC Press: Boca
Raton, FL, 2004, p. 52/1

259

Lewis, G.N.; Kasha, M. J. Am. Chem. Soc. 1945, 67, 994
Triplet olefins (excited state)
*3
R1

R4

R2

R3

Reviews:
Brand, J.C.D.; Williamson, D.G. Adv. Phys. Org. Chem. 1963, 1, 365
Stephenson, L.M.; Hammond, G.S. Angew. Chem. Int. Ed. 1969, 8, 261
Caldwell, R.A. in Kinetics and Spectroscopy of Carbenes and Biradicals, (M.S. Platz, ed.) Plenum: New York, 1990, p. 77
Wilbrandt, R.; Langkilde, F.W. NATO ASI Ser. Ser. C 1973, 410, 567
Ireland, J.F.; Wyatt, P.A.H. Adv. Phys. Org. Chem. 1976, 12, 132
Davidson, R.S. Adv. Phys. Org. Chem. 1983, 19, 1
Unett, D.J.; Caldwell, R.A. Res. Chem. Intermediates 1995, 21, 665
Tropylium ion

260
R

R

R

R

+

+
+

R

+
+
R

R

R

+
+
+

Reviews:
Harmon, K.M. in Carbonium Ions (G.A. Olah, ed.) Wiley: New York, 1973, Vol. 4, p. 1579
Lifshitz, C. Acc. Chem. Res. 1994, 27, 138
Abraham, W.; Kharlanov, V. in Handbook of Photochemistry and Photobiology, (H.S. Nalwa, ed.) American Scientific Publishers: CA, 2003, Vol.
2, p. 299
Br

Br2

+

Br-

- HBr
Br

Doering, W.v.E.; Knox, L.H. J. Am. Chem.Soc. 1954, 76, 3203 (also first use of inscribed circle to indicate aromaticity)

261
CH3

electron
impact

.

+

+ e-

Rylander, P.N.; Meyerson, S.; Grubb, H.M. J. Am. Chem. Soc. 1957, 79, 842
Vinyl cations
R2

+
R1

C
R3

Reviews:
Hanack, M. Acc. Chem. Res. 1970, 3, 209
Modena, G.; Tonellato, U. Adv. Phys. Org. Chem. 1971, 9, 185
Stang, P.J. Prog. Phys. Org. Chem. 1973, 10, 205
Grob, C.A. Angew. Chem. Int. Ed. 1972, 11, 544
Stang, P.J. Prog. Phys. Org. Chem. 1973, 10, 205
Subramanian, L.R.; Hanack, M. J. Chem. Educ. 1975, 52, 80
Hanack, M. Acc. Chem. Res. 1976, 9, 364
Rappoport, Z. Acc. Chem. Res. 1976, 9, 265
Stang, P.J.; Rappoport, Z.; Hanack, M.; Subramanian, L.R. Vinyl Cations, Academic Press: New York, 1979
Rappoport, Z. Reactive Intermediates 1983, 3, 427
Wan, P.; Yates, K. Rev. Chem. Intermediates 1984, 5, 157
Rappoport, Z.; Stang, P.J. (eds.) Dicoordinated Carbocations, Wiley: Chichester, 1997
Okuyama, T.; Lodder, G. Adv. Phys. Org. Chem. 2002, 37, 1
Okuyama, T. Acc. Chem. Res. 2002, 35, 12

262
+
H

CF3 CO2

+

CF3 COO
Cl+

Cl

Cl

Cl

Peterson, P.E.; Duddey, J.E. J. Am. Chem. Soc. 1963, 85, 2865
H+
- HOTs

+

CF3 CO2

CF3 CO2 -

+

TsO

Peterson, P.E.; Kamat, R.J. J. Am. Chem. Soc. 1966, 88, 3152
Peterson, P.E.; Duddey, J.E. J. Am. Chem. Soc. 1966, 88, 4990
Jones, W.M.; Miller, F.W. J. Am. Chem. Soc. 1967, 89, 1960
Fahey, R.C.; Lee, D.J. J. Am. Chem. Soc. 1967, 89, 2780
Nishimura, A.; Kato, H.; Ohta, M. J. Am. Chem. Soc. 1967, 89, 5083
Bly, R.S.; Ballentine, A.R.; Koock, S.U. J. Am. Chem. Soc. 1967, 89, 6993
Noyce, D.S.; Matesich, M.A.; Peterson, P.E. J. Am. Chem. Soc. 1967, 89, 6225
Ph

+
X

Ph

Miller, L.L.; Kaufman, D.A. J. Am. Chem. Soc. 1968, 90, 7282

-

+

X

263
- OOC

Ph

- OOC

H2 O
C+

X -X

- OOC

- OOC

Ph

Ph

Ph
O

OH

- CO2

- CO2
Ph

Ph

O

Grob, C.A. Bull. Soc. Chim. Fr. 1960, 1360
O

EtO
Br

+
- Br-

X

80% EtOH/H2 O
X

- H+
X

X

Grob, C.A.; Cseh, G. Helv. Chim. Acta 1964, 47, 194
Grob, C.A.; Csapilla, J.; Cseh, G. Helv. Chim. Acta 1964, 47, 1590
Huang, S.J.; Lessard, M.V. J. Am. Chem. Soc. 1968, 90, 2432
Grob, C.A.; Spaar, R. Helv. Chim. Acta 1970, 53, 2119
Grob, C.A.; Pfaendler, H.R. Helv. Chim. Acta 1971, 54, 2060
Grob, C.A.; Nussbaumer, R. Helv. Chim. Acta 1971, 54, 2528
Grob, C.A. Chimia 1971, 25, 87

X

264
OSO2 CF3

OMe

MeOH

+
R2

R1

R2

- CF3 SO3 -

- H+

R1

R1

R2

R1 , R 2 = alkyl
Summerville, R.H.; Senkler, C.A.; Schleyer, P.v.R.; Deuber, T.E.; Stang, P.J. J. Am. Chem. Soc. 1974, 96, 1100
Stang, P.J.; Deuber, T.E. Org. Synth. 1974, 54, 79
Vinylidenes (methylene carbenes, alkylidene carbenes)
R1
C

C

:

R2

Reviews:
Hartzler, H.D. in Carbenes, (R. A. Moss, M. Jones Jr.; eds.) Wiley-Interscience: New York, 1975, Vol. 2
Stang, P.J. Chem. Rev. 1978, 78, 383
Stang, P.J. Acc. Chem. Res. 1978, 11, 107
Stang, P.J. Acc. Chem. Res. 1982, 15, 348
Ph

H

KNH2 /NH3 (l)

Ph
C

Ph

Br

:

Ph

Ph

Coleman, G.H.; Maxwell, R.D. J. Am. Chem. Soc. 1934, 56, 132
Emschwiller, G. Bull. Soc. Chim. Fr. 1935, 2, 1625

Ph

+ KBr

265
Kobrich, G. Angew. Chem. Int. Ed. 1967, 6, 41
O
R

ON
N

O

:
R

R

R

Newman, M.S.; Okorududu, A.O. J. Am. Chem. Soc. 1968, 90, 4189
Newman, M.S.; Okorududu, A.O. J. Org. Chem. 1969, 34, 1220
Newman, M.S.; Din, Z. J. Org. Chem. 1973, 38, 547
R

R

OSO2 CF3

- CF3 SO3 -

R

tBuO-

+
H

R

:

- HOtBu

R

R

tBuOR

OtBu
R

R
R

Stang, P.J.; Mangum, M.G.; Fox, D.P.; Haak, P. J. Am. Chem. Soc. 1974, 96, 4562
Vinylidenecarbenes (allenylidenes, alkenylidene carbenes)

266
R1
C

C

C

:

R2

Reviews:
None.
H

K+
_

KOtBu
- HOtBu

- KCl

Cl

:

PhCH=CH2

Cl

Hartzler, H.D. J. Am. Chem. Soc. 1961, 83, 4990
Hartzler, H.D. J. Org. Chem. 1964, 29, 1311
le Noble, W.J.; Chiou, D.M.; Okaya, Y. J. Am. Chem. Soc. 1979, 101, 3244
Wallach intermediate (see Dications)
Wanzlich carbenes
Reviews:
Arduengo, A.J. III Tetrahedron 1999, 55, 14523 (imidazolylidenes and imidazolinylidenes)
Ph
N

Ph

Ph

N

N

:

2
N
Ph

N
Ph

N
Ph

Ph

267
Wanzlich, H.W.; Schikora, E. Angew. Chem. 1960, 72, 494
Wanzlich, H.W.; Schikora, E. Chem. Ber. 1961, 94, 2389
Wanzlich, H.W. Angew. Chem. Int. Ed. 1962, 1, 75
Wanzlich, H.W.; Schönherr, H.J. Angew. Chem. Int. Ed. 1968, 80, 153
Wheland Intermediates (arenium ions, benzenium ions)
R

R

R

R

+

+

+

+ E

H

+

H

H

E

E

E

R = EDG, para substitution

R

R

R

+

+ E+

R

+

H

H

H
E

E

E

+

R = EDG, ortho substitution
+

R

R

+ E+

H

H

R

R
E

E

+

R = EWG, meta substitution
Reviews:
Olah, G.A. Acc. Chem. Res. 1970, 4, 240

H
E

+

268
Wheland, G.W.; Pauling, L. J. Am. Chem. Soc. 1935, 57, 2086
Wheland, G.W. J. Am. Chem. Soc. 1942, 64, 900
Matlow, S.L.; Wheland, G.W. J. Am. Chem. Soc. 1955, 77, 3653
R
R

R

R

HBr / Al2 Br6

+

H+

H

+
R

H

H

H

H

R

H

+
R
H

R

H

+
R

H

+
R

- H+
R

H

Nightingale, D.V. Chem. Rev. 1939, 25, 329
McCaulay, D.A.; Lien, A.P. J. Am. Chem. Soc. 1951, 73, 2013
McCaulay, D.A.; Lien, A.P. J. Am. Chem. Soc. 1953, 75, 2411
Brown, H.C.; Smoot, C.R. J. Am. Chem. Soc. 1956, 78, 2176

+
H

H

+

269

Gold, V.; Tye, F.L. J. Chem. Soc. 1952, 2172 (first direct spectroscopic evidence for protonation of aromatics)
Reid, C. J. Am. Chem. Soc. 1954, 76, 3264
R

BF4 -

+

H

H

Olah, G.A.; Kuhn, S.J. Nature 1956, 178, 693
Olah, G.A.; Kuhn, S.J. J. Am. Chem. Soc. 1958, 80, 6535

+

AlCl4 -

Doering, W.v.E.; Saunders, M.; Boyton, H.G.; Earhart, H.W.; Wadley, E.F.; Edwards, W.R.; Laber, R. Tetrahedron 1958, 4, 178

270

R
R

R

NO

+
R

NO

+

NO

+

R
R

R = Me, Et, Ph
Hubig, S.M.; Kochi, J.K. J. Am. Chem. Soc. 2000, 122, 8279
Ylides (1,2-Dipoles)
Reviews:
Johnson, A.W. Ylid Chemistry, Academic Press: New York, 1966
Nesmeyanov, N.A. Mendeleev Chem. 1967, 12, 35
Lowe, P.A. Chem. Ind. 1970, 1070
Wittig, G. J. Organometallic Chem. 1975, 100, 279
Morris, D.G. in Recent Advances in the Chemistry of Ylides, (G.G. Wubbels, ed.) Butterworths: London, Vol. 10, 1983, p. 189
Lloyd, D. Non-Benzenoid Conjugated Carbocyclic Compounds, Elsevier Press: Amsterdam, 1984, p. 32
Johnson, A.W. Ylides and Imines of Phosphorus, Wiley: New York, 1993
Clark, J.S. (ed.) Nitrogen, Oxygen, and Sulfur Ylide Chemistry, Oxford University Press: Oxford, 2002
(i) Ammonium ylides
R1
_
R2

+
N

R3
R4
R5

Reviews:
Zugravescu, I.; Petrovanu, M. N-Ylid Chemistry, (translated by C. Stoicescu) McGraw-Hill International Book Co.: New York, 1976
Clark, J.S. (ed.) Nitrogen, Oxygen, and Sulfur Ylide Chemistry, Oxford University Press: Oxford, 2002

271

+
H

NMe3

+
-

NMe3

Br

_
Ag2 O

Ingold, C.K.; Jessop, A.J. J. Chem. Soc. 1929, 2357
+

+

NMe3 Br

H

NMe3

_
PhLi
- PhH
- LiBr

Wittig, G.; Felletschin, G. Ann. Chem. 1944, 555, 133
O
OH

1.
_
+

-

Me4 N X + Ph-Li

- Ph-H
- LiX

Me3N+

R1

R2

+

R1

CH2

NMe3

R2

2. H2 O

OH-

O

_
+

Me4 P X

-

+ Ph-Li

- Ph-H
- LiX

Me3P+

CH2

R1

R2
R1

R2

+ O=PMe3

272

O

+
Ph3 P-CH 3 X- + Ph-Li

_
Ph3 P+

- Ph-H
- LiX

R1

R2

+ O=PPh 3

CH2
R1

R2

Wittig, G.; Wetterling, M.H. Ann. Chem. 1947, 557, 193
Wittig, G.; Rieber, M. Ann. Chem. 1949, 562, 177; 187
Wittig, G.; Geissler, G. Ann. Chem. 1953, 580, 44

N2

:

N+

_



PhCH 2 NMe2

- N2
Bamford, W.R.; Stevens, T.S. J. Chem. Soc. 1952, 1975
Cl

Cl


+ Et2 NH

N

Cl

Cl

_

- N2

N

N+
Et

Et
H

Bonneau, R.; Liu, M.T.H. J. Am. Chem. Soc. 1991, 113, 9872

Ph

Me2N

Ph

273

West, F.G.; Glaeske, K.W.; Kevin, W.; Naidu, B.N. Synthesis 1993, 977
Ph

Ph

H

_
CHCl3



N2
NMe2

N+

- N2

-

Ph

N+

: CCl2

Cl-

Tomioka, H.; Yamada, S.; Hirai, K. J. Org. Chem. 1995, 60, 1298
(ii) Oxonium ylides
Reviews:
West, F.G.; Clark, J.S. in Nitrogen, Oxygen, and Sulfur Ylide Chemistry, (J.S. Clark, ed.) Oxford University Press: Oxford, 2002, p. 115 - 134
H

H

_ Na+
N

_

N

Ts



O

Ph

- NaTs
- N2

Ph

O+

n

n

Kirmse, W.; Kund, K. J. Am. Chem. Soc. 1989, 111, 1465
(iii) Phosphonium ylides
R1
_
R2

+
P

R3
R4
R5

Reviews:
Gruetzmacher, H.; Heim, U.; Schoenberg, H.; Pritzkow, H. Phosphorus, Sulfur, Silicon, and Related Elements 1993, 76, 281

274
_

KOH
Ph3 P+

COOEt

Ph3 P

COOEt

Cl-

Ph3 P+

COOEt

Michaelis, A.; Gimborn, H.V. Chem. Ber. 1894, 27, 272
Aksnes, G. Acta Chem. Scand. 1961, 15, 438
_

KOH
Ph3 P+

COR

Ph3 P

COR

Cl-

Ph3 P+

COR

R = Me, Ph
Michaelis, A.; Kohler, E. Chem. Ber. 1899, 32, 1566
Ramirez, F.; Dershowitz, S. J. Org. Chem. 1957, 22, 41

Ph3 P + Ph 2 CN2

Ph3 P=N-N=CPh2


- N2

Ph

+
Ph3 P=CPh 2

Ph3 P

_
Ph

Staudinger, H.; Meyer, J. Helv. Chim. Acta 1919, 2, 635
Ph

Ph
H

Ph3 P+

Br

-

Ph

+

nBuLi
- nBuH
- LiBr

Ph3 P=CPh 2

Ph3 P

Coffmann, D.D.; Marvel, C.S. J. Am. Chem. Soc. 1929, 51, 3496

_
Ph

275
+
H

PPh3

+ PPh3
_

XNH 4 OH

Pinck, L.A.; Hilbert, G.E. J. Am. Chem. Soc. 1947, 69, 723
(iv) Pyridine ylides
R1
_

R

+
N

N
_

+
N

R2

Reviews:
Zugravescu, I.; Petrovanu, M. N-Ylid Chemistry, (translated by C. Stoicescu) McGraw-Hill International Book Co.: New York, 1976
Platz, M.S.; White, W.R. III; Modarelli, D.A.; Celebi, S. Res. Chem. Intermediates 1994, 20, 175
Ph

Ph

Ph

PhNHNH2

NaOH

- H2 O
Ph

O+ I

Ph

N+ I

- H2 O
- NaI Ph

N+

_N

HN
Ph

Scheider, W.; Seebach, F. Chem. Ber. 1921, 54, 2285
Scheider, W. Ann. Chem. 1924, 438, 115

Ph

276

N+

Ar

BrO

NaOH
- H2 O
- NaBr

N+

Ar

N+

Ar

_
H

O-

H

Krollpfeiffer, F.; Müller, A. Chem. Ber. 1933, 66, 739
Krollpfeiffer, F.; Müller, A. Chem. Ber. 1935, 68, 1169
Kröhnke, F. Chem. Ber. 1935, 68, 1177
Kröhnke, F.; Heffe, W. Chem. Ber. 1967, 70, 864
Kröhnke, F. Angew. Chem. 1953, 65, 605

N+
_

Pinck, L.A.; Hilbert, G.E. J. Am. Chem. Soc. 1946, 68, 2011

O

277

N+ I

O
O

_

- N2 Ph

_

N+

Ph
H

King, L.C.; Miller, F.M. J. Am. Chem. Soc. 1948, 70, 4154
Ph
Ph
N+

Ph

Lloyd, D.; Singer, M.I.C. J. Chem. Soc. Sect. C 1971, 2941
R1
Ph

-

N+

N+
Ph

N2 +

-

O

HI

H

:

Ph

O

H

H

R2

Ph
Ph

R1 = H, Ph; R2 = H, Me
Duerr, H.; Heu, B.; Ruge, B.; Scheppers, G. Chem. Commun. 1972, 1257

I-

278
(v) Sulfimine ylides
R2

_
R1

N

S+
R3

Reviews:
None.
_
SO2 NH2

+ Et2 S

SO2 N

Et
S+
Et

Mann, F.; Pope, W.J. J. Chem. Soc. 1922, 121, 1052 (first sulfimine)
O
SO2 NH2

+

_
SO2 N

S
R

R

- H2 O

R
S+
R

Tarbell, D.S.; Weaver, C. J. Am. Chem. Soc. 1941, 63, 2939
(vi) Sulfonium ylides
R1
_
R2

+
S

R3

R4

Reviews:
Trost, B.M.; Melvin, L.S. Jr. Sulfur Ylides: emerging synthetic intermediates, Academic Press: New York, 1975
Ando, W. Acc. Chem. Res. 1977, 10, 179
Ando, W. in The Chemistry of Diazonium and Diazo Groups, (S. Patai, ed.) Wiley: New York, 1978, Chapter 9

279
Doyle, M.P. Chem. Rev. 1986, 86, 919
Padwa, A.; Hornbuckle, S.F. Chem. Rev. 1991, 91, 263
Padwa, A.; Weingarten, M.D. Chem. Rev. 1996, 96, 223
Doyle, M.P. Chem. Rev. 1998, 98, 911
Clark, J.S. (ed.) Nitrogen, Oxygen, and Sulfur Ylide Chemistry, Oxford University Press: Oxford, 2002
S+
_

Ingold, C.K.; Jessop, J.A. J. Chem. Soc. 1930, 713
SH
HN
O
O
Ph

HN

H

- N2 Ph

NH2
HN

NH2

H

Ph

_

N2 +

N

H
H

NH2

O

S+

:

_

NH2

O

S
Ph

King, L.C.; Miller, F.M. J. Am. Chem. Soc. 1949, 71, 367
(vii) Trapping of carbenes generated by flash photolysis
Reviews:
Jackson, J.E.; Platz, M.S. in Adv. Carbene Chem. (U. Brinker, ed.) JAI Press: Greenwich, CT, 1994, p. 89

- H2 O

Ph

S

280
X+

_

Griller, D.; Hadel, L.M.; Nazran, A.S.; Platz, M.S.; Wong, P.C.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1984, 106, 2227
(trapping of carbenes via ylide formation)

(CH3 )2 C=O

Np

_

O+

H

CH3 CN


Np

H

- N2

_

N+

:

N2

Np

H
Np

H

Np
N

_

N+

H

Et3 N

Np

_

+
NEt 3

H

Barcus, R.L.; Hadel, L.M.; Johnston, L.J.; Platz, M.S.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1986, 108, 3928
(trapping of carbenes via ylide formation)

281

N



N

:

N

tBu

_
tBu

tBu

- N2

Cl

N+

Cl
Cl

Jackson, J.E.; Soundarajan, N.; Platz, M.S.; Liu, M.T.H. J. Am. Chem. Soc. 1988, 110, 5595
R1
N
N

:



_

S+
R2

R1 -S-R2

N
Ph

N
H

:

- N2

- N2

Ph

R1 -S-R2

Ph

R1

_

S+

H
H

R2

Romashin, Y.N.; Liu, M.T.H.; Hill, B.T.; Platz, M.S. Tetrahedron Lett. 2003, 44, 6519
Ynols (hydroxyacetylenes)
R

OH

Reviews:
Kresge, A.J. Acc. Chem. Res. 1990, 23, 43
Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 594 (confirmation that ketene structure is not that of hydroxyacetylene)
R

OH

RCH

C

O

Meinert, R.N.; Hurd, C.D. J. Am. Chem. Soc. 1930, 52, 4540 (coining of names "ynol" and "keteno-ynol" isomerism akin to keto-enol isomerism)

282

H

OH

von Baar, B.; Weiske, T.; Terlouw, J.K.; Schwarz, H. Angew. Chem. Int. Ed. 1986, 25, 282
Hochstrasser, R.; Wirz, J. Angew. Chem. 1989, 101, 183
O


- CO
Ph

Ph

OH

PhCH

C

O

OH

Chiang, Y.; Kresge, A.J.; Hochstrasser, R.; Wirz, J. J. Am. Chem. Soc. 1989, 111, 2355
Craig, D.; Regenass, F.A.; Fowler, R.B. J. Org. Chem. 1959, 24, 240
Julia, M.; Descoins, C. Bull. Soc. Chim. Fr. 1962, 1939
Eugster, C.H.; Kuser, P. Chimia (Aarau) 1964, 18, 358
Baker, C.S.L.; Landor, P.D.; Landor, S.R.; Patel, A.N. J. Chem. Soc. 1965, 4348

283
Index
Acylium ions (oxocarbonium ions)...........................................................................................
N-Acylonium ions (acylammonium ions)....................................................................................
Alleneoxide......................................................................................................................
Aromatic pi-complexes.........................................................................................................
Charge transfer complexes............................................................................................
Sandwich complexes (metallocenes).................................................................................
Aromatic sigma complexes (see Meisenheimer-Jackson, Janovsky, Wheland).........................................
Arylium ions (see phenyl cation)..............................................................................................
Aziridinium ions.................................................................................................................
Benzyne (arynes)................................................................................................................
Betaines (phosphonium betaines).............................................................................................
Biradicals.........................................................................................................................
Thiele hydrocarbon.....................................................................................................
Chichibabin hydrocarbon.............................................................................................
Schlenk-Brauns hydrocarbon........................................................................................
Müller hydrocarbon...................................................................................................
Norrish Type I.........................................................................................................
Norrish Type II........................................................................................................
Bridged carbocations (see halonium, non-classical, phenonium).........................................................
Carbanions.......................................................................................................................
Carbanions via E1cb............................................................................................................
Carbenes (methylenes).........................................................................................................
Carbenes (singlet)...............................................................................................................
Carbenes (triplet)................................................................................................................
Carbenes (Arduengo)...........................................................................................................
Carbenes (Bertrand)............................................................................................................
Dicarbenes.......................................................................................................................
Carbocations.....................................................................................................................
Carbynes.........................................................................................................................
2,4- and 2,5-Cyclohexadienones..............................................................................................
2,4- and 2,5-Cyclohexadienimines............................................................................................
Cyclopropenyl cations..........................................................................................................
Dications..........................................................................................................................
Benzidine rearrangement...............................................................................................
Dications synthesized in magic acid..................................................................................
Violenes..................................................................................................................
Wallach intermediate....................................................................................................

1
2
2
3
4
7
8
10
10
11
18
18
19
19
20
21
23
23
25
25
27
28
34
35
36
36
37
37
43
44
44
46
47
47
47
48
49

284
Wurster salts.............................................................................................................
1,3-Dioxolenium ions...........................................................................................................
1,3-Dipoles (carbene traps).....................................................................................................
Azomethine ylide........................................................................................................
Carbonyl oxide (Criegee zwitterion)..................................................................................
Carbonyl ylide...........................................................................................................
Nitrile ylide..............................................................................................................
Thiocarbonyl ylide......................................................................................................
1,3-Dipoles (nitrene traps)......................................................................................................
Azomethines.............................................................................................................
Azonium imines.........................................................................................................
Carbonyl imines.........................................................................................................
Nitrilimines..............................................................................................................
Nitrosoimines............................................................................................................
Thiocarbonyl imines....................................................................................................
Doering-Zeiss intermediate......................................................................................................
Enols and enolates...............................................................................................................
Episulfonium ions................................................................................................................
Sulfenium ions..........................................................................................................
Sulfonium ions..........................................................................................................
Extended cumulenones..........................................................................................................
Propadienones (methyleneketenes)...................................................................................
Butatrienones............................................................................................................
Iminopropadienones....................................................................................................
Halonium ions....................................................................................................................
Hydronium ions..................................................................................................................
Iminium ions......................................................................................................................
Janovsky complex...............................................................................................................
Ketenes............................................................................................................................
Metal ketenides..........................................................................................................
Ketene zwitterions...............................................................................................................
Ketyl radicals and ketyl radical ions...........................................................................................
Meisenheimer-Jackson complexes.............................................................................................
Mercurinium ions................................................................................................................
Metal carbenoids.................................................................................................................
Nicholas cation...................................................................................................................
Nitrenes...........................................................................................................................
Dinitrenes................................................................................................................
Trinitrenes................................................................................................................

49
50
52
52
52
52
57
58
59
59
60
61
61
62
62
62
63
65
65
69
71
71
78
80
82
85
85
86
86
89
90
91
95
96
100
102
103
105
106

285
Nitrenium ions....................................................................................................................
Nitrilium ions.....................................................................................................................
Nitronium ions...................................................................................................................
Nitrosonium ions.................................................................................................................
Non-classical ions (hyperco-ordinate carbocations, sigma-bridged cations)..............................................
Oxenium ions.....................................................................................................................
Oxirene............................................................................................................................
Oxonium ions.....................................................................................................................
Acetoxonium ions.......................................................................................................
Flavinium ions...........................................................................................................
Flavylium salts..........................................................................................................
Meerwein salts...........................................................................................................
Methoxonium ions......................................................................................................
Pyrylium salts...........................................................................................................
Phenonium ions..................................................................................................................
Phenyl cation (phenylium ion, arylium ion, benzene cation)...............................................................
Phosphenium ions...............................................................................................................
Phosphonium ions...............................................................................................................
o-Quinodimethanes (o-xylylenes)..............................................................................................
p-Quinodimethanes (p-xylylenes)..............................................................................................
o-Quinonemethides and p-Quinonemethides..................................................................................
Radicals...........................................................................................................................
Carbon centred..........................................................................................................
Gomberg radical................................................................................................
Alkyl radicals...................................................................................................
Aryl radical (phenyl radical)..................................................................................
Benzoyl radical.................................................................................................
Acyl radicals....................................................................................................
Benzyl radical...................................................................................................
Koelsch radical.................................................................................................
Group IV (Si, Ge, Sn).................................................................................................
Silyl..............................................................................................................
Germyl..........................................................................................................
Stannyl..........................................................................................................
Group V (N, P).........................................................................................................
Aminyl...........................................................................................................
N-Alkoxy-N-alkylamino radicals............................................................................
Amido radicals..................................................................................................
Hydrazyl........................................................................................................

107
110
110
111
112
114
117
121
121
122
122
123
124
124
125
126
128
129
131
132
133
134
136
136
137
142
150
154
158
160
160
160
163
164
166
166
169
170
171

286
Nitroxide radicals..............................................................................................
Thioaminyl radicals............................................................................................
Sulfonamidyl radicals..........................................................................................
N-Thiosulfonamidyl radicals.................................................................................
Verdazyls........................................................................................................
Phosphinoyl radicals...........................................................................................
Phosphinyl radicals............................................................................................
Phosphoranyl radicals.........................................................................................
Thiophosphinoyl (phosphinothioyl) radicals...............................................................
Group VI (O, S, Se)....................................................................................................
Acetoxy (acetoxyl) radicals...................................................................................
Alkoxy radicals.................................................................................................
Iminoxyl radicals...............................................................................................
Nitroxyl radicals................................................................................................
Kenyon-Banfield radical......................................................................................
Peroxy radicals.................................................................................................
Phenoxy (phenoxyl) radicals.................................................................................
Sulfanyl (mercapto, thiyl) radicals...........................................................................
Sulfinyl radicals................................................................................................
Sulfonyl radicals...............................................................................................
Sulfuranyl radicals.............................................................................................
Thionitroxide radicals..........................................................................................
Thiophenoxy (phenylthio, phenylthiyl, benzenethiyl) radicals...........................................
Phenylselanyl radical..........................................................................................
Selanyl...........................................................................................................
Radical anions....................................................................................................................
Radical cations....................................................................................................................
Wurster salts.............................................................................................................
Distonic...................................................................................................................
Silylenes and germylenes.......................................................................................................
Silylium ions (silylenium ions, silicenium ions, silyl cations, silicocations).............................................
Tetrahedral intermediates........................................................................................................
Thiirenium ions...................................................................................................................
Transition metal carbene complexes...........................................................................................
Transition metal carbyne complexes...........................................................................................
Transition metal ketenyl complexes............................................................................................
Transition metal keteniminium complexes....................................................................................
Transition metal iminium complexes...........................................................................................
Transition metal silene complexes..............................................................................................

174
175
176
178
179
182
187
191
193
194
194
196
198
200
205
206
207
213
214
216
217
219
221
222
223
223
225
226
232
235
237
239
241
243
246
247
249
251
252

287
Transition metal vinyl cation complexes.......................................................................................
Transition metal vinylidene complexes........................................................................................
Transition metal vinylidenecarbene complexes...............................................................................
Triplet ketones (excited state)...................................................................................................
Triplet olefins (excited state)....................................................................................................
Tropylium ion....................................................................................................................
Vinyl cations......................................................................................................................
Vinylidenes (methylene carbenes, alkylidene carbenes).....................................................................
Vinylidenecarbenes (allenylidenes, alkenylidene carbenes).................................................................
Wallach intermediate (see Dications)...........................................................................................
Wanzlich carbenes...............................................................................................................
Wheland intermediates (arenium ions, benzenium ions)....................................................................
Ylides (1,2-dipoles)..............................................................................................................
Ammonium ylides.......................................................................................................
Oxonium ylides..........................................................................................................
Phosphonium ylides....................................................................................................
Pyridine ylides...........................................................................................................
Sulfimine ylides.........................................................................................................
Sulfonium ylides........................................................................................................
Trapping of carbenes generated by flash photolysis................................................................
Ynols (hydroxyacetylenes)......................................................................................................

254
255
257
258
259
259
261
264
265
266
266
267
270
270
273
273
275
278
278
279
281

Sponsor Documents

Or use your account on DocShare.tips

Hide

Forgot your password?

Or register your new account on DocShare.tips

Hide

Lost your password? Please enter your email address. You will receive a link to create a new password.

Back to log-in

Close