Reviews

1
Reaction Intermediates in Organic Chemistry: the "Big Picture"

John Andraos
Department of Chemistry, York University, Toronto, ON M3J 1P3
jandraos@yorku.ca
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)
+ R2
R1 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
R1
R3
R2
R4
Reviews:
Chan, T.H.; Ong, B.S. Tetrahedron 1980, 36, 2269
3
O
tBu tBu
mCPBA
tBu
tBu
H H
H
Camp, R.L.; Greene, F.D. J. Am. Chem. Soc. 1968, 90, 7349
O
O
CH3 (CO)OOH
+ OH
OAc
64% 27%
Crandall, J.K.; Paulson, D.R.; Bunnell, C.A. Tetrahedron Lett. 1968, 5063
O O
O OAc OH
HOOAc
O
O O
HO OAc O
Crandall, J.K.; Machleder, W.H. J. Am. Chem. Soc. 1968, 90, 7292
Aromatic π-complexes
4
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
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 O-
+N N+
-O 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
NC CN R1 = H, R2 = H
R1
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
OC
+ W(CO)6 Me6
W W(CO)3
- 2 CO OC - CO
CO
Me6
Manuel, T.A.; Stone, F.G.A. Chem. Ind. 1959, 1349

7
HX X = Cl, Br
Brown, H.C.; Melchiore, J.J. J. Am. Chem. Soc. 1965, 87, 5269
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 Cl
2 FeCl3
3 Fe +2 +
- 3 MgBrCl _
- FeCl2
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 R1
+
R6 R2 R6 R2 R6 R2
+ +
R5 R3 R5 R3 R5 R3
E R4 E R4 E R4
Reaction with electrophiles, E+
R1 Nu R1 Nu R1 Nu
R6 R2 R6 R2 R6 R2
_ _
_
R5 R3 R5 R3 R5 R3
R4 R4 R4
Reaction with nucleophiles, Nu-
Reviews:
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
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
Cl
- Cl- N+ H2 O
N N
Cl Cl + HO Cl
-H
- Cl-
OH
H2 O N+
N
HO OH - 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
Cl R
N
N+ R
N
Cl Cl-
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
HO OH
RO3S
∆
RO3S Cl
- RSO3 Na
- H2 O
Limpricht, H. Chem. Ber. 1874, 7, 1439

13
Br CH3 NH NH
NaOH
+ 2
- 2 HBr
Br NH2
Kym, O. J. Prakt. Chem. 1895, 51[2], 325
Cl
Cl
Cl Cl Ph2 N NPh2
2 Ph2 N- K+
+ 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)
NH2
Cl
* * *
* + 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 F Li
Ph-Li Ph-Li
- Ph-H - LiF
Li Ph
Wittig, G.; Fuhrmann, G. Chem. Ber. 1940, 73, 1197

15
O OH
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 COOH (Ph)

Ph-Li CO2
F
- Ph-H
- LiF
Huisgen, R.; Rist, H. Naturwiss. 1954, 41, 358

Huisgen, R.; Rist, H. Ann. Chem. 1955, 594, 137
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 R
RNa
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
O
O
FVP
.. O
- CO
O O O
O
benzyne
- CO
O O
O
O
O
. . +
O
- CO - CO
benzyne
O
Brown, R.F.C.; Solly, R.K. Austr. J. Chem. 1966, 19, 1045
O
hν
N Ar / 10 K N
O
- CO
- CO2
O
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
+
+ nBuLi
Br PPh3
+ PPh 3 PPh3 Br-
_
- nBuH
- LiBr ylide
+ +
O -O PPh3 -O PPh3
+ PhLi tBuOH
PPh3 _
+ Li +
_
R H - PhH - LiOtBu
R R
R - O=PPh3
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
19
OH . R2
R3
O
.. .
CH2
.
CH2 . . . .
R1
. CH2
. . . . . . . O
CH2 CH2 CH2 O
R1 C .. C R4
. R2 R3
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
Ph Ph Na or K
Cl Cl
- NaCl or
Ph Ph KCl Ph Ph
Ph 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 Ph Ph
Cl Cl
Ph Ph
Na or K
Ph
. . Ph
- NaCl or
KCl
Ph
Cl Ph Ph Cl
Ph Ph
. Ph Ph
. Ph
Na or K
- NaCl
or - KCl
Schlenk, W.; Brauns, M. Chem. Ber. 1915, 48, 661; 716
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
2 PhCOCl O O
AlCl3
Ph Cl
2 PhLi
Ph Ph Fe Ph Ph
HCl
Cl Cl HO OH
Ph Ph Ph Ph
- CuCl Cu or Ag
or AgCl
.
Ph
.
Ph
Ph 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
+ CH 2 =CH 2 + CO
O
hν .. O
Hα abstraction
C
O
α cleavage
Hδ abstraction
CHO
+ CO
Norrish Type II
*3
O
R2
hν
O
R2
Hγ abstraction OH . R2
β cleavage
OH R2
R1 R1 R1
. R1
+
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
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
24
hν
- N2
. . - CO
hν
N N
O
Dowd, P. J. Am. Chem. Soc. 1966, 88, 2587 (first observation of biradicals by ESR)
R1
R3
R1
. R3 R1
OR
R3
ROH
R2
R4
R2 . R4 R2 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 O
hν CH2 =CH 2
. .
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.; 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 NMe4
_
Ph Ph 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 + H2O NMe3
+ H 3 O+
Ar Ar
_ +
NMe3
+ NMe3
Ar Ar
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
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
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
CH3 OH : CH2
Dumas, J.B.; Peligot, E. Ann. Chim. Phys. 1835, 58, 5 (attempt)
Regnault, H.V. Ann. Chim. Phys. 1839, 71, 427
base
CHCl3
- HCl
: CCl2
Geuther, A. Ann. Chem. 1862, 123, 121 (suggestion)
∆ : CH2
CH2 I2 :
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
hν or ∆ hν or ∆ C
:
R1 R2
R1 R2 - N2 - 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 -
CCl3 - :CCl2 + 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 R R R
Y Y
X 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 COOR
RO H
- N2 RO :
N2
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
+ Ph 2 C=CPh 2
T = 77 K Ph Ph
N2
:
254 nm
Ph Ph
Ph Ph - N2
H
R-H
. .
Ph Ph + R
T > 77 K
32
Gibbons, W.A.; Trozzolo, A.M. J. Am. Chem. Soc. 1966, 88, 172 (matrix isolation EPR)
N2
.
:
H
hν 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
hν .. λ(max) = 300 nm
benzene Ph Ph
Ph Ph
hν
H
. λ(max) = 340 nm
cyclohexane Ph Ph
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
N2 _
N+
:
hν
H
Np H
Np H - N2 Np
N _ N+
Et3N Np
+
_
NEt 3
H
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
O O O .
R R R R R R
hν
R R
- N2
R
.. R R
. R
R = H, F
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 R2
Reviews:
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)
KOtBu
:
+ THF
N N N N
- KCl
Cl- - tBuOH
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 N2
THF
- 78o C
+ (iPr2 N)2 PCl N(iPr)2
Me3Si Li Me3Si P
- LiCl
N(iPr)2
37
N2
_
:
N(iPr)2 + N(iPr)2 N(iPr)2
N(iPr)2 hν
Me3Si P Me3Si P
Me3Si P Me3Si C P
- N2
N(iPr)2 N(iPr)2
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
. .
:
:
hν
- 2 N2
Trozzolo, A.M.; Murray, R.W.; Smolinsky, G.; Yager, W.A.; Wasserman, E. J. Am. Chem. Soc. 1963, 85, 2526
N2 N2
:
Ph Ph hν Ph Ph
- 2 N2
Wasserman, E.; Murray, R.W.; Yager, W.A.; Trozzolo, A.M.; Smolinksy, G. J. Am. Chem. Soc. 1967, 89, 5076
Carbocations
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.; 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)
H2 O
Cl acid catalyst OH
Stieglitz, J. Am. Chem. J. 1899, 21, 101
Ph Ph H2 SO4
Cl MeO C Cl MeO C+ HSO4 -
+ AlCl3 + AlCl4 - - HCl
Ph Ph Ph Ph 3 3
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
40
Ph Ph Ph
Cl H2 SO4
HSO4 - SO4 -2
Ph Ph Ph + Ph +
HCl 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 + NH2 fuchsine
-
X X-
H2 N H2 N
41
Me2N Me2N
+
NMe2 + NMe2 crystal violet
- -
X X
Me2N Me2N
Kehrmann, F.; Wentzel, F. Chem. Ber. 1901, 34, 3815

Baeyer, A.; Villiger, V. Chem. Ber. 1902, 35, 1189
Baeyer, A. Chem. Ber. 1905, 38, 569
Baeyer, A. Chem. Ber. 1905, 38, 1156
H2 O
80% EtOH OR
Cl
Ph - Cl- Ph + Ph
Cl OR R = H, Et
H2 O +
80% EtOH
Ph Ph - Cl- Ph Ph Ph Ph
42
Ward, A.M. J. Chem. Soc. 1927, 445; 2285

+ NaOH
Ph-CH 2 Ph OH
Ph Cl
- Cl- - Na+
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
+ + Cl
H+ Cl-
Cl-
- Cl-
Cl Cl
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

43
O O
+ SbF 5 + SbF 6 - Me3 C+ SbF 6 -

tBu F tBu - CO
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
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
R
.
C
:
Reviews:
Connor, J.A. J. Organometallic Chem. 1975, 4, 235 (carbenes and carbynes)
Hg +2
N2
_
hν
Hg + 2 N 2 + 2 EtOOC
.
C
:
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
R O
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
R2
H
H
45
Reviews:
None
Cl
NH2 N
F F F F
2 tBuOCl
- 2 tBuOH
F F F F
R Cl
R
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
O
O
COOH H2 O / O
pTolSO2 Cl pTolSO2 O alumina
H2 N O
N - pTolSO2 NH 2
- HCl
- 2 H+
- 2 e-
Coutts, I.G.C.; Edwards, M.; Musto, D.R.; Richards, D.J. Tetrahedron Lett. 1980, 21, 5055
R2
tBu tBu tBu O R3

R1 R2 H +
R1 H
+ R1
N+ R3 N
R2 N
O
O- tBu
tBu 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 R3 R2 R3 R2 R3 R2 R3
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 Cl Ph OtBu
N2
tBuOH
+
- N2 - HCl
Ph Cl
Ph Ph Ph Ph
Ph
Ph
Ph Ph
Ph
H2 O O HBF 4
+ BF4 -
Ph
Ph Ph Ph Ph
Breslow, R. J. Am. Chem. Soc. 1957, 79, 5318

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 NH2 NH2
H
+ + - 2 H+
H2 N NH2 H2 N NH2
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/ O O
SbF 5 /SO2
(CH2)n (CH2)n +O C (CH2)n C O+ [SbF 6 -]2
- 2 H2 O
HO OH H2 O OH2
+ +
48
Olah, G.A.; Comisarow, M.B. J. Am. Chem. Soc. 1966, 88, 3313
FSO3 H/ R1
R1 R1
SbF 5 /SO2 +
N OH H N+ OH2 H N+ + [SbF 6 -]2
- H2 O
R2 R2 R2
Olah, G.A.; Calin, M. J. Am. Chem. Soc. 1968, 90, 943
R
R R R
FSO3 H/
X SbF 5 /SO2
R = H, Ph
+2 [SbF 6 -]2
X - 2 HX X = Cl, Br
R 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
- e- - e- + +
R2 N CH CH CH CH
n
NR2 R2 N CH CH CH CH
n
.
+
n
NR2
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
+ +
N N
Ph + + OH
2 H+ + H2 O
Ar N N+ Ar N N Ar N N Ar N N OH
- H2 O + +
-H -H
O- H
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
Cox, R.A.; Fung, D.Y.K.; Csizmadia, I.G.; Buncel, E. Can. J. Chem. 2003, 81, 535
(v) Wurster salts
+ +
H2 N NH2
50
Me2N NMe2
Br2
Me2N NMe2
.
+
+ Br-
HOAc
Wurster's blue
Me2N NH2
Br2
Me2N NH2
.
+
+ Br-
HOAc
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
NMe2
.
+ NMe2 + NMe2
- e- - e-
NMe2 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
Br + AgBF4 + BF4 - + AgBr
O
O
Meerwein, H.; Wunderlich, K. Angew. Chem. 1957, 69, 481
Cl
Cl
O Ph O Ph
+ -
Cl N2 BF4 + +
H
+ BF4 - Cl H
O O
Cl
Cl
Meerwein, H.; Allendorfer, H.; Beckmann, P.; Kunert, F.; Morschel, H.; Pawellek, F.; Wunderlich, K. Angew. Chem. 1958, 70, 211
O R O R
+ AgBF4 + Et-Br + BF4 - + AgBr + Et-H
O O
Meerwein, H.; Hederich, V.; Wunderlich, K. Arch. Pharm. 1958, 291, 541
O O H
+ - + Ph 3 CH
+ Ph 3 C BF4 + BF4 -
O O
52
Meerwein, H.; Hederlich, V.; Morschel, H.; Wunderlich, K. Ann. Chem. 1960, 635, 1
1,3-Dipoles
carbene traps
+
+ R1 R2
X _ R1
R1 X R3 +
+ _
:
_ O R1 C N
R5 R2 R3
R4 R2 O-
R2
R4 R3 carbonyl oxide 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

(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
+ _ hν
Ph2 C=N=N N2 + Ph 2 C :
+ _
Ph2 C : + O2 Ph2 C=O-O
+ _ + _
Ph2 C=O-O + Ph2 C=N=N 2 Ph2 C=O + N2
R R R
MeOH
O+ O- + O O- MeO OOH
R R R
dimerization CH2 =O
R O
R O O R R
O O
R O O R
Bartlett, P.D.; Traylor, T.G. J. Am. Chem. Soc. 1962, 84, 3408
54
+ _ RCHO Ph O R
hν
Ph2 CN2 Ph2 C-O-O
- N2 Ph H
O O
Murray, R.W.; Suzui, A. J. Am. Chem. Soc. 1971, 93, 4963
N
+
R 1 R N R O- R O R'
+ O2 R'-CHO
_ O+
N N
- N2 R H
R R O O- R O O
- N2
R N
N N2 O + R2 C=O
R
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
hν mCPBA ∆ or hν
+ _
Ph O+ Ph
Ph Ph Ph O Ph
Ph
55
Arnold, D.R.; Karnischky, L.A. J. Am. Chem. Soc. 1970, 92, 1404
O Ph O+
Ph hν _
Ph Ph
O+ _
O hν 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 O
O+ COOEt
Ph CN
Ph O+ CN
_
_
Ph CN Ph CN
CN
COOEt
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
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
O+ NC CN
_ PhC CPh
Ph Ph
Ph Ph CN CN
Ph Ph
Hamsberger, H.; Huisgen, R. Chem. Commun. 1971, 1190
O O O O
N2
Cu : _
MeOOC-C C-COOMe
- N2 COOMe
O O O+ O
OMe OMe OMe MeO

COOMe
Ueda, K.; Ibata, T.; Takebayashi, M. Bull. Chem. Soc. Jpn 1972, 45, 2779
57
hν O
N2 tBuOH matrix/
Ph O+ Ph O
- 196 C Ph Ph
:
Ph Ph _
Ph Ph - N2 Ph Ph
Ph 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
CN NO2
H
N NEt3
_
Ph N+ Ph N
+ -
- Et3 NH Cl
Ph Cl NO2
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
N N
hν CH3 CN + _ A B
CH2 N2 : CH2 CH3 N CH2
- N2
A B B A
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
R1 Ar R1
Cl R2 + hν
_
Ar N
N
- HCl
N R2
R2
Ar
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)
59
R O
_
S R
O
S+ + O
R
O
R 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 R2
N N S
_
R1 R2 - N2 R1 S+ R2 R3 R4
S
R3 C CR4
R1 S R2
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
60
tBu
S
S+ tBu
tBu tBu _
Ph Ph
:
+ S S+ Ph
Ph Ph _
Ph
McGimpsey, W.G.; Scaiano, J.C. Tetrahedron Lett. 1986, 27, 547
nitrene traps
R2
+ + _
R1 X R3
: nitrilimines
: :
R1 C N N
N
:
_ R2
R2 +
R1 N N azonium imines
carbonyl imines (X = O)
: :
thiocarbonyl imines (X = S) N R3
azomethine imines (X = N-R) _
+
R1 N O
: :
nitrosoimines
N R2
_
(i) Azomethines
Reviews:
Boyer, J.H. Mechanisms of Molecular Migrations 1969, 2, 267
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 hν 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 CN
hν
+ N+
- N2
NC CN 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
(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 R3 R
H
O X H O
R
R1
63
HOOC
CH3 CH3 CH3

MeOH Me H OMe Me Me
O
O O O O
Et HiPrCH HiPrCH
O 2 Et O - ArCOO- 2 Et H
Ar
- ArCOOH - MeOH
- OMe- - MeOH
CH3 CH3 Me
Me
O+ O+
HiPrCH iPrCH 2 Et H
2 Et
- H+ - H+
CH3 CH3
CH2 iPr iPrCH 2
MeO Et Et OMe
Doering, W.v.E.; Zeiss, H.H. J. Am. Chem. Soc. 1953, 75, 4733
Enols and Enolates
OH O-
R3 R3
R1 + H+
R1
R2 R2
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 S+ Br- CH3 Br + CH 3 SCH 2 CH2 Br

Br
S+ Br- S
CH3 SCH 2 CH2 Br CH3 Br +

Cahours, A. Compt. Rend. 1865, 60, 620; 1174
Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267
H2 O
Cl Cl Cl OH
ClCH2CH 2 S+
S S
- Cl-
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+ -
Cl
S+ S
EtS EtS OH2 - H2 O Et
OH
+ 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
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
100 %
S H2 SO4 O2N
Cl 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-SH
R-S+ + R'-S-S-R' R-S-S-R' + R'-S+
R-S+ + R'-SH 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 - OH-
SH S S+
O
COOH Br Br
Ph-Br
- H+ - H2 O
S S
Gilman, H.; Diehl, J.W. J. Org. Chem. 1959, 24, 1914

69
X1 X2 X1 X2
Ph S COOH Ph S+ + X3 _ COOH
X X3 X
X2 , X3 = H, Ph
Iskander, Y.; Tewfik, R. J. Chem. Soc. 1961, 2393
Ar S Ar
_
R + R-S +
Ar Ar
Ar = p-O2 N-C6 H4
Iskander, Y.; Riad, Y. J. Chem. Soc. 1961, 2397
SO3 - Ag+ SO3 - +SCH3 SO3 -
O2N NO2 O2N NO2 O2N NO2

N
+ CH 3 Br
- AgBr
N+
NO2 NO2 NO2 SCH3
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
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+ I-
von Oefele, A. Ann. Chem. 1864, 132, 82
Me
PhCH 2 SCH 2 Ph + MeI S+ I- PhCH 2 I + PhCH 2 SMe

PhCH 2 CH2 Ph
Me
S+ I-
PhCH 2 SMe + MeI PhCH 2 Me PhCH 2 I + Me2 S
Me2 S + MeI Me3 S+ I-
Schöller, C. Chem. Ber. 1874, 7, 1274

71
3 EtSH + HI Et3 S+ I- + H 2 S
Cahours, A. Compt. Rend. 1875, 80, 1317

Cahours, A. Compt. Rend. 1875, 81, 1163
Collier, H.B.; Allen, D.E. Can. J. Res. 1942, 20B, 284
Et
CH3 NO3 + MeSEt S+ NO3 - EtNO3 + Me2 S

Me Me
Me2 S + CH 3 NO3 Me3 S+ NO3 -
O2N O2N
Me3 S+ NO3 - + HO NO2 Me2 S+ - O NO2

- HNO3
O2N 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
PhNH 2
O PhCH=CH(CO)NHPh
430 C
PhCH PhCH=C=C=O
- CO2 PhCH=CHCOOMe
O - acetone dimerization MeOH
O
O
- CO2
- CO 550 C
- acetone
PhCH CHPh
PhC CH
O
Brown, R.F.C.; Eastwood, F.W.; Harrington, K.J. Austr. J. Chem. 1974, 27, 2373
73
Ph O Ph Ph
560 C
C C O C : Ph H
- CO2 - CO
H O - acetone H H
Brown, R.F.C.; Eastwood, F.W.; Harrington, K.J.; McMullen, G.L. Austr. J. Chem. 1974, 27, 2393
O O
O O H
495 C
+ C C O
- CO2 H
O O
- acetone
O
O O mCPBA
O
CH2 =C=C=O O
O
COOH O
H2 O O
O
- acetone - CO2 540 C
O O O O O O - acetone
O
CH2 =C=O C O
: - 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
74
COOMe COOMe
254 nm
+ C C O
N MeOH N
O
Mazzocchi, P.H.; Bowen, M.W.; Kachinsky, J. Chem. Commun. 1977, 53
O
FVT
(CH2 )n (CH2 )n C C O
- CO2
O - acetone
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
CH=CH2 HOOC-CH=CH2 + CH 2 =C=C=O

H 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 CH
N2 O
major
C O CH2 =C=C=O + CO2
O O 650 C
- N2
O O minor
O=C=C=C=O + CH2 =O
Chapman, O.L.; Miller, M.D.; Pitzenberger, S.M. J. Am. Chem. Soc. 1987, 109, 6867
1. SOCl2
R1 Br R1
2. [Ph3 P-N=PPh3 ]+ [Mn(CO)5 ]-
C C O + Mn(CO)5 Br + [Ph 3 P-N=PPh3 ]+ Cl-
R2 COOH R2
R1 Br R1
[Ph3 P-N=PPh3 ]+ [Mn(CO)5 ]-
C C O + Mn(CO)5 Br + [Ph 3 P-N=PPh3 ]+ Cl-
R2 COCl R2
R1 = Me, Ph, H; R2 = Me, Ph, Me R1
O
R1 R2
2 C C O
R2 R1
O
R2
Masters, A.P.; Sorensen, T.S.; Tran, P.M. Can. J. Chem. 1987, 65, 1499
76
O :
- CO2
- CO
O
- CO2 CO
O
C
C C O
:
77
O
O
O
O FVP FVP
C C O
- CH2 =CH 2 - CO2
O O
- CO2 - acetone
O
- acetone O
- CF3 COOH
O
- CH2 =CH 2
O
CF3
O
- CH2 =CH 2
O
O
CF3 C C O
H O - CF3 COOH
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
F O
C C O
F
F
2
Brahms, J.C.; Dailey, W.P. J. Am. Chem. Soc. 1989, 111, 3071
78
O
F F
FVP
O C C O
- CO2
F F
Brahms, J.C.; Dailey, W.P. J. Am. Chem. Soc. 1989, 111, 8940
R
O R
R FVP
O + C C O
O - N2
R
N2
Brahms, J.C.; Dailey, W.P. Tetrahedron Lett. 1990, 31, 1381
S O S
FVT
C C O
- CO2
S O - acetone S
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
FVP
O CH2 =C=C=C=O + CF 3 COOH
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 X
X FVP
+ 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
C C C O
- H2 O - CO
- CH2 =O
COOH 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
O O
R
RNH O
NH FVP FVP
N R-N=C=C=C=O
O R1 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 C RN=C=C=C=O
- HX - CO2
X O O
- acetone
O O
- CO2 FVT
R = Ph, iPr, tBu
- acetone
X = SMe, NMe2 , OMe, tBu-NH
O RN
RN C C O
[1,3]-X
X 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
X = SMe, Cl, NMe 2 , NEt 2 , OMe
Plug, C.; Frank, W.; Wentrup, C. J. Chem. Soc. Perkin Trans. 2 1999, 1087
82
Ar-NH O
R1 O
O
_
N NHAr N+ N-Ar
R-N=C=C=C=O
N N N N
O O
Ar O
NH
N
O N
Shtaiwi, M.; Wentrup, C. J. Org. Chem. 2002, 67, 8558
Halonium Ions
X +
R1 R4
X = Cl, Br, I
R2 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+ Br COOH HOOC Br

Br2 Br-
HOOC COOH HOOC COOH HOOC Br Br COOH

COOH Br+ COOH Br COOH
Br2 Br-
HOOC 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
I+ Cl I
ICl
COOH Cl-
CH3 CH CHCOOH
COOH
Ingold, C.K.; Smith, H.G. J. Chem. Soc. 1931, 2742
Roberts, I.; Kimball, G.E. J. Am. Chem. Soc. 1937, 59, 947
84
Br+ Br Br
Br2 + + MeOH
- Br- Ph 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 Cl+
Cl2 - OOC Cl
- Cl- O
COO - COO -
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
+
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
H2 O + HBr H3 O+ Br- (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
O O2N
O2N
NaX
+ _ R Na+
R - HX
NO2 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
hν or ∆ R2
R2
C C O
R1 R1
- N2
:
R2
N2
O
Ph
Ph Zn
Cl C C O
Cl - ZnCl2
Ph
Ph
Staudinger, H. Chem. Ber. 1905, 38, 1735

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

Wilsmore, N.T.M.; Stewart, A.W. Chem. Ber. 1908, 41, 1025
88

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.; 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 .. O
O
hν
H
89
O
O
H
H
hν
RO RO
Quinkert, G.; Wegemund, B.; Blanke, E. Tetrahedron Lett. 1962, 221
O
O
hν
CHCl2 CHCl2
Cl O Cl
hν O
Cl Cl
Cl Cl
Cl Cl
Chapman, O.L.; Lassila, J.D. J. Am. Chem. Soc. 1968, 90, 2449
Metal Ketenides
C C O
Reviews:
None.
90
O O O
Ag O
pyridine
2 + C C O + 3
O- Ag+ O
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- R1 O- R1 O- R1 O-
+
R2 N R2 N+ R5 R2 P+ R5 R2 S+ R4
R3 R4 R3 R4 R3
91
Reviews:
None.
EtOOC EtOOC
+ R
C C O R N+
EtOOC N EtOOC _
O
Gompper, R.; Wolf, U. Ann. Chem. 1979, 1388
O
O N2 NH
C N
-O
+
C
hν + N NH
- N2
Pacansky, J.; Chang, J.S.; Brown, D.W.; Schwarz, W. J. Org. Chem. 1982, 47, 2233
O -O N+
C C
N
- O3S - 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
OH O-
R1
. R2 R1
. R2
+ H+
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+ - O Ar
Na or
Ar Ar
Mg-MgI2
Ar
. Ar
Ar
Ar O- Na+
Ar
O O- K+
KOH Ar
Ar
Ar
Ar
O 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- K+ O
KOH/
O O EtOH
O O
O O .
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 O - K+
Ph + Ph KOH
Ph 2 Ph
Ph Ph
O OH O .
Scholl, R. Chem. Ber. 1899, 32, 1809
Scholl, R.; Hahle, H. Chem. Ber. 1923, 56B, 918
94
O O - [MgBr]+
Ar Ar
+ Ph 3 C-MgBr
. + Ph 3 C .
Ar Ar
O - [MgBr]+ O - [MgBr]+
2
Ar
. 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
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 R1 R2 R1 R2
O2N NO2 O2N NO2 O2N NO2
_ _
NO2 NO2 NO2
O-
O- R1 R2 R1 R2
R1 R2
N+ O2N NO2 N NO2
O2N +
-O
O-
N NO2
NO2 +
-O 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 O-
O
H S
O2N NO2
Na2 SO3 O2N NO2
- 2 Na+
NO2
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 R4
R2 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
HgOAc R HgOAc R
R
Hg(OAc)2 Hg+ - H2 O NaBH4
OAc
- OAc- - HOAc
HO - Hg HO
R AcO
R - B(OH)3
- NaOAc
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
Hg+ X HgX
ROH -
X
OR
98
Traylor, T.G.; Baker, A.W. J. Am. Chem. Soc. 1963, 85, 2746
H
MeO MeO+
H+ - MeOH I-
CH2 CH2 + HgI 2
HgI HgI + HgI
I- I-
MeO MeO+
H+ - MeOH
CH2 CH2 + HgI 2
_ HgI _ HgI 2 HgI 2
2
I- I-
MeO MeO+
H+ - MeOH - I-
CH2 CH2 + HgI 2
_ HgI 3 _ HgI 3 _ 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
99
OAc
Hg+
PhCH 2CH CH2 + Hg(OAc)2 OAc-
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
HgX
Hg+
HgX 2 ROH H+
C 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 R2 R1 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
O O
∆ O
ROH
Cu
Ph Ph
- N2 Ph
:
N2 H OR
Cu
Yates, P. J. Am. Chem. Soc. 1952, 74, 5376

101
Li
R-Li + CH2 Cl2 H
R-H +
Cl
Cl Cl
Li
RCH=CH 2
:
H
- LiCl Cl H
Cl Cl
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
102
O- Li+ Cl
O- Li+ O- Li+
O
:
Ph-O- Li+
MeLi + CH2 Cl2
- LiCl Cl H Cl
- LiCl
- Me-H
Cl
MeLi
- LiCl
Cl Cl
Me Me
Li LiCl
MeLi MeLi
:
Li MeLi Li
Ph Cl - Me-H Ph Cl - LiCl Ph Cl
Ph Cl - LiCl Ph Me
- LiCl
- LiCl
- MeLi
Ph Cl Ph Me
Closs, G.L.; Coyle, J.J. J. Org. Chem. 1966, 31, 2759
Nicholas cation
103
R2
+
R1 R3
(CO) 3Co Co(CO)3
Reviews:
Nicholas, K.M. Acc. Chem. Res. 1987, 20, 207
R2 R2 R2
OH Nu
+
R2 Co2 (CO)8 R1 R3 R1 R3
Nu- R1 R3 R2
H+ [O]
R1 OH R1 Nu
- 2 CO
R3 - H2 O
(CO) 3Co Co(CO)3 (CO) 3Co Co(CO)3 (CO) 3Co Co(CO)3 R3
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
Nitrenes
..
:
R N R N
:
singlet triplet
Reviews:
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
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
Gritsan, N.P.; Platz, M.S. Adv. Phys. Org. Chem. 2001, 36, 255
O O
O
R R'OH
Br
: :
R NH - HBr R N N C O
RNH OR'
O R2 + H2O R1 NH 2 + CO2 + R2 COOH

R1 NH
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
H Ph
: :
N Ph3 C N N
Ph3 C X - HX
Ph Ph
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
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
Reviews:
Nimura, S.; Yabe, A. in Magnetic Properties of Organic Materials, (P.M. Lahti, ed.) Marcel Dekker: New York, 1999, Chapter 7, p. 127
hν : :
: :
: :
: :
N3 N3 N N N N
- 2 N2
Trozzolo, A.M.; Murray, R.W.; Smolinsky, G.; Yager, W.A.; Wasserman, E. J. Am. Chem. Soc. 1963, 85, 2526
: :
N3 N
hν CN
- 2 N2
: :
CN
N3 N
Hall, J.H. J. Am. Chem. Soc. 1965, 87, 1147
106
N3 N3
hν
..
N
..
N
:
- 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 X N
septet
Reviews:
None.
N3
..
N
..
N
NC CN NC CN NC CN
hν
N3 N3
77 K
- N2 N3 N3
- 2 N2
..
N
..
N
CN CN 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
N3
..
N
..
N
..
Oda, N.; Nakai, T.; Sato, K.; Shiomi, D.; Kozaki, M.; Okada, K.; Takui, T. Synth. Met. 2001, 121, 1840
hν hν hν
.. .. ..
- N2 HCN + NC-N=C=N-CN
- N2 - N2
N3 N3 N3 N3 N N3 N 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
OH + OH2 Ph
H + +
H2 O
N N N N+ Ph2 C=O + Ph-NHR
:
- H2 O
:
Ph3 C R Ph3 C R Ph3 C R Ph2 C R

108
Cl Ph
+
H2 O
N N N+ Ph2 C=O + Ph-NHR
- Cl-
:
Ph3 C R
:
Ph3 C R Ph2 C 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)
NaOCl MeOH
+
NH N - Cl- N N N
Cl +
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
MeO N
N +
N N
+
Cl
Cl-
Cl N
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 Ac H
N N N
HI
I-
SO4 -2
+ - I2
- SO4 -2
Y 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+ N
- SO4 -2 +
Ph 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
OH R2
OH O O O OH
N P2 O5 N P P N+ -O O O
P P
O O
R1 R2 R1 R2 O O
R1
R2
R2
N O
N
OH R2
R1 O O O - P2 O5 R1 NH
R1 OH
P P
O O
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 O
Reviews:
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.; 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
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 + AcO
1 - 1
- OBs + +
2 2 6
6
[1,2-H] HOAc
III
+ +
[1,6-H]
HOAc
[1,6-H]
OAc
OBs - OBs- + 1
1 + + 2
2 6
6
II I 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
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 + tBu
Bartlett, P.D. J. Chem. Educ. 1953, 30, 22

114
OTs
+
H+
- OTs-
Heck, 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
. R3
O O+ O R1
R1 tBu
+
.
N C
R3 R1 tBu
+
_
N C
R3 R1
tBu
N
C R4
O R3
R4 R4 N R4
R2
R2 R2 R2
Rieker, A. Tetrahedron Lett. 1969, 2611

115
NO2 NO2
O2N MeO
O
Ph-OMe
N+ O NO2 OMe +
- pyridine +
BF4 - O2N
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 O+ O
OH OH
NH H+
- TsNH 2 +
H Ph Ph
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- RO+ + 2 e-
Bursey, M.M.; Hass, J.R.; Harvan, D.J.; Parker, C.E. J. Am. Chem. Soc. 1979, 101, 5489
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 O- AlCl3
Ph
AlCl3
N O N + Ph-O+
O O
Uto, K.; Miyazawa, E.; Ito, K.; Sakamoto, T.; Kikugawa, Y. Heterocycles 1998, 48, 2593
O O
OH O
tBu tBu CH3 CN tBu tBu tBu tBu

tBu tBu Br2
KBr H2 O
+
tBu OH
R tBu tBu
tBu
Hegarty, A.F.; Keogh, J.P. J. Chem. Soc. Perkin Trans. 2 2001, 758
117
O O O+
H2 O OH
O OH
Ph
N3
- OAc- N3 -
+ HO N3 +
Ph OAc Ph Ph
Ph
Novak, M.; Glover, S.A. J. Am. Chem. Soc. 2004, 126, 7748
Oxirene
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
O
CrO3
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 O
hν or ∆ R2
R2
R1 R1 R1 R2
- N2
:
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* hν C* C*
- N2
:
N2
hν
C* C O C* O :
Me2 C* + CO + Me2 C : + C*O
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
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
O O O
O
hν
R2
* R2 * R1
R1 - N2 R1 * * R2
R1 R2
:
N2
R1 R1
O C O C *
*
R2 R2
ROH ROH
O R1
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
O .
+ O
N
- HCN - HCN
N
- CO2
O O
Hop, C.E.C.A.; Holmes, J.L.; Terlouw, J.K. J. Am. Chem. Soc. 1989, 111, 441
Oxocarbons
O _2
_2
_2 O O O _2
O O O
O O
O O
O O
O O O O O
deltate squarate croconate 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 _4
HO OH KOMe O O
MeOH 4 K+
HO OH O 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 Name
+ H H pelargonin
HO O H OH cyanidin
R2
- OH OH delphinidin
Cl OMe OMe enidin (malvidin, syringidin)
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 Me
+ +
O X- O X- X = BF 4 , SbCl 6 , AuCl4 , Bi 2 I7 , HgI3 , picrate,
Et Et Me Me 1/2 SnCl6 , 1/2 PtCl6
Cl
O
3 + 4 Et2 O...BF3 + 2 Et2 O O B + 3 Et3 O+ BF4 -
Cl
EtO
3
124
Me2 O + BF3 + Et-F O+ BF4 -

Et
O-
O2N NO2
Et3 O+
NO2
Meerwein, H.; Hinz, G.; Hofmann, P.; Kronig, E.; Pfeil, E. J. Prakt. Chem. 1937, 147, 257
O RO 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 OH
O+ + H2 O
OMe
- Br- OMe
+
Br
Winstein, S.; Ingraham, L.L. J. Am. Chem. Soc. 1952, 74, 1160
(vi) Pyrylium salts

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+
O O O
∆ H3 O+ HX
X-
2 COOEt - 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
Gastaldi, C. Gazz. Chim. Ital. 1921, 5, 169
R2
HClO4 R1
O O R3 O
R2
+
R1 R3 + 2 R - H2 O
4 O R4 R4 OH
R4 O+ R4
ClO4 -
Balaban, A.T.; Nenitzescu, C.D. Ann. Chem. 1959, 625, 74
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
+
+ +
R4 R1 R4 R1 R4 R1 R4 R1
R1 R4
+ +
R2 R3 R2 R3 R2 R3 R2 R3 R2 R3
Reviews:
None.
Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3863

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
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
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 + + X-
- N2 X
R 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 R
.
N2 +X
-
- N2
+ . + etc.
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
R1 R2
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, 49-
50, 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 R2 N
LiAlH4
P Cl P+ P H R = iPr, Et
- -
- Cl "H "
R2 N R2 N R2 N
R R R
N N N
LiAlH4
P Cl P+ P H R = tBu
- -
- Cl "H "
N N N
R R R
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 N
AgPF6
-
P+ Cl P+ PF 6 - + AgCl
N N
tBu tBu
tBu tBu
N Cl N
AgPF6
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+ OR
R'
Reviews:
130
Smith, D.J.H. Organophosphorus Chem. 1972, 4, 1

Allen, D.W. Organophosphorus Chem. 1977, 8, 1
Smith, D.J.H. in Comprehensive Organic Chemistry, (I.O. Sutherland, ed.) Pergamon Press: Oxford, 1979, Vol. 2, p. 1127 - 1187
Cristan, H.J.; Plenat, F. in Chemistry of Organophosphorus Compounds, (F.R. Hartley, ed.) Wiley: Chichester, 1994, p. 45 - 183
Stephan, D.W. Angew. Chem. Int. Ed. 2000, 39, 501
131
CH3 CH3
CH3 O P OCH3 + CH 3 I CH3 O P+ OCH3 I- CH3 O P O

- CH3 I
OCH3 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
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 Br
CHBr2
2 NaI
. Br
CHBr2
- 2 NaBr
- I2 . 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 p-xylene
CH3 CH3
-2H . CH2 CH2
n
Szwarc, M. Nature 1947, 160, 403

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
Ar
2 nBuLi Ar
HO I Li+ -O Li O
- nBuI Ar
- nBuOH
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 hν 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
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
Ph
Cl
Ph
Zn
Ph
. Ph
+ Cl .
Ph Ph
Ph Ph
2
Ph
. Ph
Ph H
Ph
Gomberg, M., J. Am. Chem. Soc. 1900, 22, 757

137
Gomberg, M. Chem. Ber. 1900, 33, 3150

Gomberg, M. Chem. Ber. 1901, 34, 2726
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
hν
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
∆
R4 Pb R. . + 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
CH4 + Cl2 CH3 Cl, CH 2 Cl2 , CHCl 3 , CCl 4
Pease, R.N.; Walz, F. J. Am. Chem. Soc. 1931, 53, 3728
Cl2 C=CCl2 + 1/2 O2

Cl3 C Cl
Dickinson, R.A.; Leermakers, P.A. J. Am. Chem. Soc. 1932, 54, 3852
Br
HBr
Br Br (absence of O2 )
HBr
Br Br 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
hν
CH2 C
n
COOMe COOMe
Melville, H.W. Proc. Roy. Soc. London 1937, 163A, 511
O Ph
Ph O
O
Brodie, B.C. Ann. Chem. 1858, 108, 79
O Ph
Ph O
O
R H + 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
hν
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
hν
R H + + HCl
Cl Cl R Cl
O O
hν
R H + Cl
+ HCl + CO
Cl R Cl
O
OH
HBr
Br
Zn
.
2 2 2 Ph Ph
- H2 O ZnBr2 Ph
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
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 OEt
O
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 Ph
- N2
2 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 2 tBu-O .
CH3 + 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
N CH3 + 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
Ph
N Ph N N O
- N2
Ph . .
+ OAc
Ph-H
Ph-Ph + HOAc
O
NO

Waters, W.A. J. Chem. Soc. 1937, 113
O2N N N O - Na+ + O2N N N O

R Cl
- NaCl O
O2N N N O
O - N2
O2N . .
+
O
O
R
Ph-H
O2N +
O
Ph HO R
R
Kühling, O. Chem. Ber. 1895, 28, 41

Kühling, O. Chem. Ber. 1896, 29, 165
144
X . .
+ X
R1 R1
2 .
R1 R1 R1
Cu Cu+2 + 2 e-
.
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
- + + N 2 + HX
Ar1 N2 + X Ar2 H Ar1 Ar2
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 4 Ph . + Pb
Ph . . + Ph Ph-Ph
2 Ph . + Hg Ph2 Hg
145
Dull, M.F.; Simons, J.H. J. Am. Chem. Soc. 1933, 55, 3898
Ph Br + Na (g) Ph . + NaBr
Horn, E.; Polanyi, M. Z. Physik. Chem. 1934, 25B, 151
Ph N N CPh3 + Ph-H
- N2
Ph . + Ph 3 C . Ph-H
Ph-Ph + Ph3 CH
Ph O
O Ph 2
O
. - CO2
Ph . + PhCOO . Ph-H
Ph-Ph + PhCOOH
Ph O
..
O
Ph N N OAc Ph + OAc
- N2
PhCH 2 N N OAc
- N2
PhCH 2 .. + OAc
NO
N Ph-Ph + N2 + CH 3 COOH
+ Ph-H
Ph
O
NO
N PhCH 2 Ph + N 2 + CH 3 COOH
+ Ph-H
PhCH 2
Grieve, W.S.M.; Hey, D.H. J. Chem. Soc. 1934, 1797 (homolytic aromatic substitution)
Hey, D.H. J. Chem. Soc. 1934, 1966
146
Ph2 Hg + Ph-NH-NH-Ph
150 C
Ph . 2 Ph-H + Hg + Ph-N=N-Ph
Ph4 Pb + S
150 C
Ph . Ph-S-S-Ph + PbS
Ph4 Sn + S
150 C
Ph . 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 Ph
Ph O
O
R H + SO2 Cl2 R Cl + SO2 + HCl + 2 CO2 + 2 PhCl
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1939, 61, 2142; 3432
N2 + Cl-
+ Ph
- N2
N - HCl 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
- N2
Ar . + Me2 N . R-H
Ar-R + Me2 NH
Elks, J.; Hey, D.H. J. Chem. Soc. 1943, 441

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 4 Ph . + 4 CO2 + Pb
Ph . + Ar-H Ph-Ar + H .
Hey, D.H. Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1954, 2747
Ph NHPh Ph NHPh Ph NPh

LiAlH4 H2 O2
N NH N
Ph Ph Ph
decalin
Ph-H + Ph2 CH-CHPh 2
Ph NPh
major
N
Ph2 CH2
Ph 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 . + Ag + Ph 3 PbNO3
OH
Ph . + EtOH Ph-H + .
2 Ph . Ph-Ph
H
Spice, J.E.; Twist, W. J. Chem. Soc. 1956, 3319
O(CO)Ph
Ph I
- PhI
O
.
Ar-H
PhCOOAr + H .
Ph O
O(CO)Ph
- CO2
Ph . Ar-H
Ph-Ar + H .
Hey, D.H.; Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1956, 1475
PhNHNH2
Ag2 O
- H2 O
Ph N N H
- N2
Ph . .+ H Ph-H
- 2 Ag Ar-H
Ph-Ph Ph-Ar + H .
Hardie, R.L.; Thomson, R.H. J. Chem. Soc. 1957, 2512
149
O O
Ph N N C Ph
H +
Ph N N . .
+ C Ph
CH3 OH
O
Ph N NH + CH3 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 OH
tBu tBu
hν
tBu tBu
+ Br .
Br
.
150
OH OH OH O .
tBu tBu tBu tBu tBu tBu tBu tBu
+ +
. Br Br
Lappin, G.R.; Zannucci, J.S. Tetrahedron Lett. 1969, 5085
Ph-N=O
308 nm
Ar 12 K
Ph ..
+ 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
.
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
Ph Cl
+ Zn 2
Ph
. + ZnCl2
O O O
2
Ph
. + 1/2 O2
Ph O Ph
Norris, J.F.; Franklin, D.R. Am. Chem. J. 1903, 29, 141 (suggestion)
O O
Ph Ph
hν
Ph
. + Ph .
O
O
2
Ph
. Ph
Ph
2 Ph . Ph-Ph
O
Glazebrook, H.H.; Pearson, T.G. J. Chem. Soc. 1939, 589
. + N N
Ph
.N N
Ph
Ph
Ph Ph O
Ph
152
Kharasch, M.S.; Zimmerman, M.; Zimmt, W.; Nudenberg, W. J. Org. Chem. 1953, 18, 1045
. + Ph-CHO
O
.
Ph Ph O Ph
. + N
. N
O
Ph
Ph
Kharasch, M.S.; Schwartz, D.; Zimmerman, M.; Nudenberg, W. J. Org. Chem. 1953, 18, 1051
O
O
Ph N
N Ph ∆
- N2
2
Ph
.
O
Mackay, D.; Marx, U.F.; Waters, W.A. J. Chem. Soc. 1964, 4793
O O
Br
hν
- 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
tBuO
O
O
OtBu 2 CO2 + 2 tBuO .
O
tBuO . + Ph-CHO tBuOH + Ph-C=O

.
.
Ph-C=O + R-N=O
O
R
Ph N
O .
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 2I ..
Ph-CHO + I . Ph-C=O + HI
.
Ph-C=O + I2
Ph
C O + I .
I
Solly, R.K.; Benson, S.W. J. Am. Chem. Soc. 1971, 93, 1592
O
O
Ph
Ph hν
Ph
. . +
Ph
OR OR
154
O O O .
Ph
. +
tBu
N
Ph
N Ph
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
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
hν
2 . COCl
1o
(COCl)2
hν
. COCOCl + Cl .
155
. COCl CO + Cl .
. COCOCl 2 CO + Cl .
2o RH + Cl . R . + HCl
R . + (COCl)2 RCOCl + . COCl
. COCl CO + Cl .
Kharasch, M.S.; Kane, S.S.; Brown, H.C. J. Am. Chem. Soc. 1942, 64, 1621
hν
. .
.
(CH3 )2 C=O CH3 + CH 3 -C=O
.
.
CH3 -C=O
CH3 -C=O + O2
CO + CH3
CH3 COO + O . .?
. CH3
CH3 + (CH 3 )2 C=O CH4 +
. O
. CH2
CH3
.CH2
O + O2
.
CH3 COOH + H-C=O
. CH3 + O2 H-C=O + H2O

156
.
H-C=O CO + H .
.
H-C=O + O2 CO2 + OH .
H . + O2 HOO .
Marcotte, F.B.; Noyes, W.A. Jr. J. Am. Chem. Soc. 1952, 74, 783
tBu-O-O-tBu 2 tBuO .
tBuO . CH3 +. (CH 3 )2 C=O
.
..
CH3 + CO CH3 -C=O
tBuO . + CO tBu + CO2
Porter, G.B.; Benson, S.W. J. Am. Chem. Soc. 1953, 75, 2773
O O O
N N
- N2
2 .
Cramer, R. J. Am. Chem. Soc. 1957, 79, 6215
. k1
.
RCHO
-H . RCO CO + R
. . Cl
k2 CCl4 H
RCOCl + . CCl3 RH RCl

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

+ H
O O
R X
+ nBu3 Sn . . + nBu3 Sn-X
R
O O
R
. . + H
R H
O
R
. R. + CO
R . + nBu3 Sn-H R-H + nBu 3 Sn .

O 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
hν
Ph Ph Ph + Ph-CH 2
Ph
O
. .
CO + Ph-CH 2
.
Ph-CH 2 + Ph-CH 2
. PhCH 2 CH2 Ph
.
Ph-CH 2 + O2 .
. .
Ph-CH 2 O-O
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 + 6 NaCl
(PhCH 2 )3 As + 3 PhCH 2 Cl (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
hν CH2 Br
CH3
Br2
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 PhCH 2 + + Cl-
2 PhCH 2 + + Fe 2 PhCH 2 . + Fe+2
2 PhCH 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
R3
.
Si
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 SiH3
∆
2 H3 Si .
H3 Si SiH2 SiH3
∆
H3 Si . + H3 Si SiH2 .
H3 Si SiH2 . H3 Si . + H 2 Si :
Emeleus, H.J.; Reid, C. J. Chem. Soc. 1939, 1021 (pyrolysis of disilane and trisilane)
(CH3 COO)2 Cl3 Si

Cl3 SiH +
5
(CH3 COO)2
5
2 CH3 COO . hν
CH3 COO CH3 . + CO2
CH3 . + HSiCl3 CH4 + Cl3 Si .

162
R-CH=CH 2 + Cl3 Si . .
R-CH-CH 2 SiCl3
.
R-CH-CH 2 SiCl3 + HSiCl3 R-CH2 -CH2 SiCl3 + Cl3 Si
.
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 CH + Cl3 SiH
SiCl3
via Cl3 Si .
(PhCOO)2
RCH CH2 + Cl3 SiH RCH 2
Burkhard, C.A.; Krieble, R.H. J. Am. Chem. Soc. 1947, 69, 2687
F F Me
hν Me CF2 Me CF2 CF2
Me2 SiH2 + Si CF2 H Si CF2 CF2 H Me Si CF2 CF2 H
H H
F F Me CF2 CF2 H
Me
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)
tBuO-OtBu
hν
2 tBuO .
. .
tBuO + (Me3 Si)3 SiH
. O .
tBuOH + (Me3 Si)3 Si
(Me3 Si)3 Si + RNO2 N Si(SiMe3) 3
O . R O
R
N
O
Si(SiMe3) 3 R-N=O + (Me3 Si)3 SiO .
(Me3 Si)3 SiO . + (Me3 Si)3 SiH (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
R3
.
Ge
R2
Reviews:
164
tBuO-OtBu
hν
2 tBuO .
tBuO . + Me3 GeH Me3 Ge . + tBuOH
Me3 Ge . +
Me3Ge
.
Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79
(iii) Stannyl
R1
R3
.
Sn
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)
R'-CH=CH2 + R3 Sn . .
Jackel, G.S.; Gordy, W. Phys. Rev. 1968, 76, 443
R'-CH-CH2 SnR3
.
R'-CH-CH2 SnR3 + R3 Sn-H R'-CH2 -CH2 SnR3 + R3 Sn .
Neumann, W.P.; Albert, H.J.; Kaiser, W. Tetrahedron Lett. 1967, 2041
165
.
R2 Sn :+ R 2 Sn : R3 Sn + RSn :
R = (Me3 Si)2 CH
Davidson, P.J.; Hudson, A.; Lappert, M.F.; Lednor, P.W. Chem. Commun. 1973, 829
tBuO-OtBu
hν
2 tBuO .
tBuO . + nBu3 SnH nBu3 Sn . + tBuOH
nBu3 Sn . +
nBu3Sn
.
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
R3 Sn-SnR 3
hν
2 R3 Sn .
R3 Sn . + S
S R3 Sn
S
. S
S S
166
S R3 SnS
R3 Sn . +
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 iPr
iPr Sn Sn iPr 2 iPr Sn .

3 3 3
iPr 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
Ph3 C .
∆
2 Ph2 NH
PbO2
Ph2 N-NPh2 2 Ph2 N . 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 R1 R1 R1
2 N NH2
HgO
N N N N
- N2
2 N .
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
O2N N
O OtBu - CO2
O2N
.
N
R
+ tBuO .
O
Pedersen, C.J. J. Org. Chem. 1958, 23, 255

168
NH2
.
NH
tBu tBu
R. tBu tBu
tBu tBu
Atherton, N.M.; Land, E.J.; Porter, G. Trans. Faraday Soc. 1963, 59, 818
Ph Ph Ph
N N N N
hν
77 K
N2 + 2 N .
O O CCl4 O
Ph
Ph
N Cl hν N . .
+ Cl
O 77 K O
CCl4
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
hν
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
NH + 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+3 + H 2 O2 Ti+4 + OH- + HO . .

R1 OH R1 O
R1 OH
HO . + N HO
.
N HO NH
R2 R2
R2
Smith, P.; Fox, W.M. Can. J. Chem. 1969, 47, 2227

170
R
O
O
hν . N
NH O tBu R OtBu
Danen, W.C.; West, C.T. J. Am. Chem. Soc. 1971, 93, 5582
.
tBu-O-O-tBu 2 tBu-O
.
NH
+ tBuO . tBuOH +
N
R
CH3 -N=N-CH3
OtBu
N2 + 2 CH 3 . R OtBu
.
R
NH
OtBu
+ CH 3 . CH4 +
R
N
OtBu
Danen, W.C.; West, C.T.; Kensler, T.T. J. Am. Chem. Soc. 1973, 95, 5716
(iii) Amido radicals
R2
R1
Reviews:
.
N
Goosen, A. South African J. Chem. 1979, 32, 37
O O
Cl hν
R2 + . R1
tBu
R2
Me
R1 N
R2
R1
.
N
Cl
Me tBu
171
Danen, W.C.; Gellert, R.W. J. Am. Chem. Soc. 1972, 94, 6853
OtBu
R
.
N
Koenig, T.; Hoobler, J.A.; Mabey, W.R. J. Am. Chem. Soc. 1972, 94, 2514
O O
Br + e- (aq) + Br-
CH3
O
NH
O
CH3
.
NH
OH
CH3
.
NH CH3
.
N
_
+ H+ CH3 N .
Fessenden, R.W. Chem. Lett. 1974, 29, 364
.
(iv) Hydrazyl
N R3
R1 N
R2
Reviews:
Nelsen, S.F. ACS Symp. Ser. 1978, 69, 309
172
2 Ph2 N-NHPh
PbO2 .
2 Ph2 N-NPh
Ph
N N
Ph
Ph3 C . NO
Ph2 N NPh2
Ph
Ph
Ph2 N N
Ph2 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 NO2Ph
N Ph -O
.
+
N Ph .. . +
N Ph
O2N
.
N
-O
N+ N O2N
.. N
_
NO2 NO2 NO2
Turkevich, J.; Oesper, P.F.; Smyth, C.P. J. Am. Chem. Soc. 1942, 64, 1179 (dipole moment measurement)
173
Ph
hν
.
N Ar
Ar N 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 Ph KMnO4 N Ph
nBu4 N+ Br-
O2N NH O2N
.
N
NO2 NO2
Brown, K.C.; Weil, J.A. Can. J. Chem. 1986, 64, 1836
R1
O
P
.N N
R2 R1
OEt
Et
R2
Me
Me
OEt H, tBu
R2 OPh H, tBu
R1 Et H, tBu
Tordo, P. NATO ASI Ser. Ser. C 1986, 189, 191
R R
X N
R
NH P
O
OEt
tBuO-OtBu
X N
R .
N
O
P OEt
hν
R OEt R OEt
R R
X = O, CH2 ; R = H, Me
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 O-
KMnO4 or
PbO2
KNO2 + 2 KHSO 3
- KOH K+ - O3 S
N
SO3 - K+ K+ - O3 S
.
N+
SO3 - K+
Fremy, E. Ann. Chim. Phys. 1845, 15[3], 408; 459
.
HN HN HN
NH NH NH
NH
. NH NH
.
N N+ N+
O O- O-
Piloty, O.; Schwerin, B.G. Chem. Ber. 1901, 34, 1870; 2354
175
HN NH HN NH
NH HN NH HN
N+
N N
N+
.N+
N N
.
N+
O- -O O- -O
Piloty, O.; Vogel, W. Chem. Ber. 1907, 36, 1283
NH HN NH HN
. .
. .
N+ N+ N N
O- -O O O
Niementowski, S. Chem. Ber. 1910, 43, 3012

Kuhn, R.; Blau, W. Ann. Chem. 1958, 615, 99
(vi) Thioaminyl radicals
S R2
R1
.
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
R1
.
(vii) Sulfonamidyl radicals
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 O
K+ - O S O O S O - K+
NH2
O O
- K2 SO4 , - H2 SO4
.
NH NH
SO2 SO2 SO2
Dewar, P.S.; Forrester, A.R.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 1 1972, 2862
.N OR
tBu SO2
Teeninga, H.; Engberts, J.B.F.N. Rec. Trav. Chim. Pays-Bas 1978, 97, 59
X X X
O O
K+ - O S O O S O - K+
NHOMe
O O
- K2 SO4 , - H2 SO4
.
N-OMe N-OMe
SO2 SO2 SO2
Forrester, A.R.; Johansson, E.M.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 1 1979, 1112
178
Y
hν
Y
.
tBuO
Y
RSO 2 N
Br
RSO 2
.
N
- tBuOH
RSO 2 N Y = alkyl, alkoxy
.
H
tBu
tBuO . tBu
. O
RSO 2 N
H
- tBuOH
RSO 2
.
N RSO2 + tBu-N=O
RSO 2
N
tBu
Teeninga, H.; Zomer, B.; Engberts, J.B.F.N. J. Org. Chem. 1979, 44, 4717
R R
hν
MeSO2 N
Cl
- Cl . MeSO2 N
. R = Me, Et, CHMe2
Danen, W.C.; Gellert, R.W. J. Am. Chem. Soc. 1980, 102, 3264
R1
.
(viii) N-Thiosulfonamidyl radicals
N R2
SO2 S
Reviews:
None.
179
SAr
SO2 N hν
SAr
SAr
SAr PbO2 .
SO2 N
SO2 N
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 Ph Ph Ph Ph Ph
N N N N
PhNH N
N N-Ph
MeI
N N
N N-Ph
[O]
HN 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
180
2
Ar1
N NH2 +
Ar1 O
2
Ar1
N NH CH
Ar1
[O]
2
Ar1
N
.
N CH
Ar1
Ar2 Ar2 Ar2 Ar2 Ar2 Ar2
Ar1 Ar1
N N CH
Ar2 Ar2 2
Kuhn, R.; Neugebauer, F.A. Monatsh. Chem. 1963, 94, 1
Ar1
2 N NH2 + HC(OEt)3
BF3
Ar1
N N CH NH N
Ar1
[O]
Ar1
N N CH
.
N N
Ar1
Ar2 Ar2 Ar2 Ar2 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 Ph
N N
Ph
H
Ph
N
.
N
N
N N
N
Ph (CH2) 4 Ph
.
N N
.
N N
Ph
H
Ph
N N Ph
.
N N Ph
Kuhn, R.; Fischer-Schwarz, G. Monatsh. Chem. 1966, 97, 517

181
Ph
.
N
. N
Ph Ph
_
N
_
N
Ph
N N N N N N+ N
N+
N N N N
n
n
Ph Ph Ph Ph
R1 R1 R2
R2
R1
Ph N Ph
Ph Ph
N
R1 =
.
N
N
N
N
R2 =
. 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
R3 O
R1 R1 R1 R1
N N N N
N N . N N .
R2 R2
Neugebauer, F.A. Angew. Chem. Int. Ed. 1973, 12, 455

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
R1
.P
R2
Reviews:
Rachon, J. Pol. J. Environ. Studies 1996, 5, 62
O
O O
∆
OR RO
RO P
OR
P OR
2
RO
.
P
OR
RO
P O P OR
OR
O
R = Et, nPr, nBu
Michalski, J.; Stec, W.; Zwierzak, A. Chem. Ind. 1965, 345
O O
R
.P
R
R = NMe2 , Et, Me(CH 2 )5
EtO
.
P
Et
Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989
183
O O O
RO P OH
γ-rays
RO P . RO P .
OR OR 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
X
.
P
X
Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)
tBuO O
O OtBu
2 tBuO . + 2 CO2
.
O O
RO P H + tBuO RO P . + tBuOH
OR OR
184
RO
O
P . +
CN
.
CN
O P S-tBu
OR S-tBu
RO OR
Stella, L.; Merenyi, R.; Janousek, Z.; Viehe, H.G. J. Phys. Chem. 1980, 84, 304
O O O
O
hν
P Ph
R
. +
Ph
.
P
Ph
R Ph
O O
. + N O . N O
R
R
O
O
Ph .
P
Ph + N 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 O O
R1 C P R2
hν
R1 C . . + P R2
R3 R3
O O O O
R1 C P OR2
hν
R1 C . . + P OR2
OR3 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
Ph O Ph
Ar P
Ph hν
Ar
. . + P
Ph
O O
R-X
O COOMe
Ph
Ph
P
. X
Ph
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 O O
Ar C P C Ar
hν
Ar C . .
+ P C Ar
R R
O2
. O-O
O
P
O
C Ar
O O
Ph-SH
- Ph-S . H P
R
C Ar
O O
. P C Ar
Br-CCl3
. Br
O
P
O
C Ar
R
- Cl3 C
CH2 =CHCOOR'
R
R'OOC
. O O
P C Ar
N+ N+ O
+ P
O
C Ar +
.N N+
Jockusch, S.; Turro, N.J. J. Am. Chem. Soc. 1998, 120, 11773
187
O O
O P Ph
Ph
O .. P
Ph
Ph O O
PPh2
hν
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
hν
Ph P . . + CH2 -Ph
Ph Ph
Zhao, N.; Neckers, D.C. J. Org. Chem. 2000, 65, 2145
(ii) Phosphinyl radicals
R1
.
P
R2
Reviews:
Bentrude, W.G. Ann. Rev. Phys. Chem. 1967, 18, 283
O
O
O
O
O . + CO2 + CH 3 .
O
188
CH3. + PCl3 CH3 -Cl + . PCl2
. .
R-CH=CH 2 +
.
PCl2
R-CH-CH 2 -PCl2 + R-CH=CH2

R-CH-CH 2 -PCl2
.
R-CH-CH 2 -CHR-CH 2 -PCl2
.
R-CH-CH 2 -PCl2 + PCl3 R-CHCl-CH2 -PCl2 + . PCl2
.
R-CH-CH 2 -CHR-CH 2 -PCl2 + PCl3 R-CHCl-CH2 -CHR-CH 2 -PCl2 + . PCl2
Kharasch, M.S.; Jensen, E.V.; Urry, W.H. J. Am. Chem. Soc. 1945, 67, 1864
NC N N CN
- N2
2 NC .
NC . + R2 P-H NC H + R2 P .
+ R2 P . R2 P
. R2 P
. + R2 P .
- R2 P. R2 P-H
R2 P
=
R2 P
189
.
Pellon, J. J. Am. Chem. Soc. 1961, 83, 1915
P
R = Cl, Br
R R
Andrews, L.; Frederick, D.L. J. Phys. Chem. 1969, 73, 2774 (IR spectra in solid Ar matrix)
Ph
P P
Ph
hν
2
.
P
Ph Ph
Ph Ph
Wong, S.K.M.; Wan, J.K.S. Spectrosc. Lett. 1970, 3, 135
R
. P
R
R = NMe2 , Et, EtO, Me(CH2 )5
R3 P
60
77 K
Co γ-rays
R2 P + R . .
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
hν
Ph2 P . .
+ Ph
Cook, W.T.; Vincent, J.S.; Bernal, I.; Ramirez, F. J. Chem. Phys. 1974, 61, 3479
190
tBu-O-O-tBu
hν
2 tBuO .
R
P P
R
+ tBuO . tBuO
R
.
P P
R
.
P +
R
P
R R tBuO R
R R R R
R = OEt, NMe2
Griller, D.; Roberts, B.P.; Davies, A.G.; Ingold, K.U. J. Am. Chem. Soc. 1974, 96, 554
P(OR)3
60
Co γ-rays
77 K
. P(OR)2 + RO .
Kerr, C.M.L.; Webster, K.; Williams, F. J. Phys. Chem. 1975, 79, 2650
Me3Si
Cl
P SiMe3 Na Me3Si
.
P SiMe3
N N N N
- NaCl
SiMe3 SiMe3 SiMe3 SiMe3
Me3Si
Cl
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
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
. Fe(CO)4 .
Me3Si P SiMe3
Me3Si P SiMe3
+ Fe2 (CO)9 + Fe(CO)5
SiMe3 SiMe3
SiMe3 SiMe3
. (CO) 3Co Co(CO)3

.
Me3Si P SiMe3
Me3Si P SiMe3
+ Co2 (CO)8 + 2 CO
SiMe3 SiMe3
SiMe3 SiMe3
Cowley, A.H.; Kemp, R.A.; Wilburn, J.C. J. Am. Chem. Soc. 1982, 104, 331
(iii) Phosphoranyl radicals
R .
P R
R
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
hν .
Hoffman, F.W.; Ess, R.J.; Simmons, T.C.; Hanzel, R.S. J. Am. Chem. Soc. 1956, 78, 6414
..
Br3 CH
.
Ph3 P + Br 2 CH
Br2 CH + Br
Ph3 P-CHBr 2
.
Ph3 P-CHBr 2 + Br3 CH
+ .
[Ph3 P-CHBr 2 ]Br- + Br2 CH
Ramirez, F.; McElvie, N. J. Am. Chem. Soc. 1957, 79, 5829
R-S-S-R 2 R-S . .
.
R-S
. + P(OEt)3
R-S-P(OEt)3 R . +
R-S-P(OEt)3
S=P(OEt)3
R-S. . + R 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
hν
.
tBuO-OtBu
.
2 tBuO
.
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
hν
2 tBuO .
OR
+ tBuO . tBuO
RO
.
P OR .
tBu + O
OR
P OR
P
RO OR RO 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
(iv) Thiophosphinoyl (phosphinothioyl) radicals

S
R1
.
P
R2
194
Reviews:
None.
S S
R P Cl
hν
R P . + Cl .
R R
S S O .
R P . + tBu-N=O R P N
R R tBu
Karlsson, H.; Lagercrantz, C. Acta Chem. Scand. 1970, 24, 3411
EtO
.
P
OEt
Group VI centred radicals (O, S, Se)
Oxygen centred radicals:

(i) Acetoxy (acetoxyl) radicals
R .
O
Reviews:
195
None.
O
Ph O
O Ph 2
O
. - CO2
2 Ph .
Ph O
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 . (slow)
. CO + CH3 . (fast)
Szwarc, M.; Taylor, J.W. J. Chem. Phys. 1955, 23, 2310

196
.
S O
S
O
N . +
O R
N
O R R . SR O
N
+
. 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+
O-OH
Fe(CN)6 -4
-3
O . + H2O
- Fe(CN)6
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 OH
hν
O . + HO .
O . + O OH O O . + OH
Zwolenik, J.J. J. Phys. Chem. 1967, 71, 2464

198
O O 2 O .
Niki, E.; Kamiya, Y.; Ohta, N. Bull. Chem. Soc. Jpn 1968, 41, 1466
O . O
+ CH 3 . β-scission
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 O
. R1 R2
N N t-Bu Me
i-Pr i-Pr
or PbO2 i-Bu i-Pr
R2 or AgO R2
Fedtke, M.; Mitternacht, H. Z. Chem. 1964, 4, 389

199
R1 OH
Pb(OAc)4
R1 O .
N N
R2 R2
Lemaire, H.; Rassat, A. Tetrahedron Lett. 1964, 2245
R1 OH
Ce(NO3 )4
R1 O .
N N
NH 4 (NO3 )
R2 R2
Thomas, J.R. J. Am. Chem. Soc. 1964, 86, 1446
R1 OH PbO2 R1 O
.
N N
R2 R2
Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. (Phys. Org.) 1966, 86
N
OH
Pb(OAc)4 N
O .
N
OH
N
.
O NO
.
_
Pb(OAc)4
Ar Ar
Ar OAc
200
Lown, J.W. J. Chem. Soc. B 1966, 441
R OH R OH
.
+ R O .
N N N
+ Br2 - .- 2 Br-
+ H+
NH 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
H2 O
OH O .
[O]
Ar1 N O + Ar2 -MgX N N
- HOMgX Ar Ar2 Ar1 Ar2
1
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 + Zn
2 RO N+ OR
ClO4 -
O-
RO N OR
Meyer, K.H.; Gottlieb-Billroth, H. Chem. Ber. 1919, 52, 1476

Meyer, K.H.; Reppe, W. Chem. Ber. 1921, 54, 327
NO
HO
N
Ph . O
N
Ph
PhMgBr [O]
Hückel, W.; Liegel, W. Chem. Ber. 1938, 71, 1442

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 HN
. .
. .
N+ N+ N 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
∆
N2 + 2 R
.
R N N R
203
tBu
.
R + tBu-N=O N O
.
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 . O
N O O N
O .
C C
(CH2) 6
O O
O NH NH O
OH
HN O NH MnO2
. O
N O N
O .
NH NH NH NH
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 N
R1 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 [O] R'MgX R [O] R

RMgX
R
N+ N+ N N
.
N+ H R' R'
O- OH O- OH O
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 Ph O .
N+
O . Ph
N O
N
Ph
Ph
206
Ph CH2 -
N+
O Ph
-O
NH + N+
Ph OH - H2 O
-O
OH O.
Ph N Ph N
[O]
Ph 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
R
O
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 OH
hν
O . + HO .
O . + O OH 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
HO t-Bu
K3 [FeIII(CN)6 ]
. 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 . OH OH O .
Ph Ph tBu tBu Ph Ph tBu tBu
+ +
Ph tBu Ph tBu
Dimroth, K.; Kalk, F.; Sell, R.; Schlömer, K. Ann. Chem. 1959, 624, 51
209
tBu tBu tBu tBu
HO CH2 OH
PbO2
ether
O CH O .
tBu tBu tBu 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
tBu
tBu O .
Yang, N.; Kastro, A. J. Am. Chem. Soc. 1960, 82, 6208
210
OH O . O . OH
tBu tBu tBu tBu tBu tBu tBu tBu
+ +
tBu tBu tBu tBu
Kreilick, R.W.; Weissman, S.I. J. Am. Chem. Soc. 1962, 84, 306
OH
O . tBu O tBu OH
tBu tBu
R2 H .
-H . O
tBu
R2
- tBu . O R2
R1 R1 R1
Matsuura, T.; Nishinaga, A.; Cahnmann, H.J. J. Org. Chem. 1962, 27, 3620
PhOH
H2 O2 / Ti+2
PhO .
Dixon, W.T.; Norman, R.O.C. Proc. Chem. Soc. 1963, 97 (ESR of phenoxy radical)
211
NMe2
tBu
. O N
tBu
NMe2
Neuhoeffer, O.; Heitmann, P. Chem. Ber. 1963, 96, 1027
I HO
.O
COOH
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
.
O
NO2
.
N tBu
OH
tBu
NO2
NH tBu tBu
NPh2 NPh2
+ +
O2N NO2 O2N NO2
Ayscough, P.B.; Russell, K.E. Can. J. Chem. 1967, 45, 3019
O . OH OH .
O
tBu tBu tBu tBu
+ +
R R
tBu tBu
O . O . O
tBu tBu tBu tBu
R
tBu O
tBu
Mahoney, L.R.; DaRooge, M.A. J. Am. Chem. Soc. 1970, 92, 890
213
OH O .
tBu tBu tBu tBu
1/4 PbO2
- 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 = H, p-MeO, p-Me2 N, p-COOEt, p-Ph, o-OH

R
214
Schmidt, U.; Müller, A.; Markau, K. Tetrahedron Lett. 1963, 1091
tBuO-OtBu
hν
2 tBuO .
tBuO . + MeSH MeS . + tBuOH
MeS . +
MeS
.
R'-S-S-R'
hν
2 R'-S .
S R
+ R'-S . . S S-R'
R R
R
Alberti, A.; Bonini, B.F.; Pedulli, G.F. Tetrahedron Lett. 1987, 28, 3737
(ii) Sulfinyl radicals
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
.
OH
.
Ar-S-S-Ar + HO Ar
.
S SAr
- H+
- ArS-
Ar-S=O
Ar-SH + HO . Ar-S
. H2 O2
Ar-S-OH
HO. . Ar-S=O
- H2 O
Ar-S(O)Cl
hν .
Ar-S=O + Cl .
.
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
HS NH
COOH HS COOH
O
cysteine 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
.
2 RSO2 R
O
S O
O
S R
. .
R-S=O + R-SO2 -O
2 R-S=O
. R S O
O
S R RS
O
. .+ RSO2 R S
O
S R
R-SO2 -O
. . + RSO2 R
O
S O
O
S R
O
O O
R = Ph
. .
Bennett, J.E.; Brunton, G.; Gilbert, B.C.; Whittall, P.E. J. Chem. Soc. Perkin Trans. 2 1988, 1359
.
R-OO + R'-SH
.
R-OOH + R'-S
R'-S
R'-S-O-O
+ O2
. + R'-SH
R'-S-O-O
.
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
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
hν
2 tBu-O .
.
tBu-O + Et3 SiH tBuOH + Et3 Si .
.
Et3 Si + Ph-SO2 Cl
.
Et3 Si-Cl + Ph-SO2
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
R2
.
S
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
hν
RO . .
+ Cl
RO . + SF4
.
RO-SF4
218
Gregory, A.R.; Karavelas, S.E.; Morton, J.R.; Preston, K.F. J. Am. Chem. Soc. 1975, 97, 2206
OMe
MeO . +
MeO
S
OMe MeO
.
S
OMe
Cooper, J.W.; Roberts, B.P. Chem. Commun. 1977, 228
O-SiMe3
R
.
S R
Me3 Si-O . R
+
S R R R
R R
Me3 Si-OH +
R
. S R
R R
Gara, W.B.; Roberts, B.P. J. Organometallic Chem. 1977, 135, C20
O-CMe3
R
.
S R
Me3 C-O . + R S 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
hν
SMe
. S .
O
O
tBu
- tBuO . O
O
O 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
S-CF3
CF3 S . R1 .
S
R2
O S
S(CO)Et
. R1 R2
Et
O
S
R1 .
S
R2
. S(CO)tBu
tBu S
R1 .
S
R2
Giles, J.R.M.; Roberts, B.P. J. Chem. Soc. Perkin Trans. 2 1980, 1497
(v) Thionitroxide radicals
R1
N S .
R2
220
Reviews:
None.
∆
N S S N 2 N S .
∆
O N S S N O 2 O N S .
Bennett, J.E.; Sieper, H.; Tavs, P. Tetrahedron 1967, 23, 1697
∆
N S S N 2 N S .
-O Ph -O Ph
N S S N +
N+
O
. N S . +
N+
O N
N N S
Ph Ph
Danen, W.C.; Newkirk, D.D. J. Am. Chem. Soc. 1976, 98, 516
221
N S S N
hν
2 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 hν
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)
Ph Se
Se Ph
hν
2 PhCH 2 Se .
Ph
Se
Se
Ph hν
2 Ph-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
.
R-CH-CH 2 -SePh + O2 .
R-C(OO )H-CH2 -SePh
Ito, O. J. Am. Chem. Soc. 1983, 105, 850

223
Ph-Se-Se-Ph 2 Ph-Se .
Ph-Se . + R COOMe
PhSe
.
COOMe PhSe
.
R R COOMe
PhSe COOMe PhSe 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
224
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
-2
2 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
+A
NC CN .
_
+ A+ .
NC CN NC CN
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 + e- tBu-NO2
_
.
tBu-NO2 .
_
NO2 - + tBu .
tBu-NO2 .
_
.
+ tBu tBu-N=O + tBuO-
tBu-N=O + tBu . (tBu)2 N-O .

(tBu)2 N-O . .
+ tBu (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
Werst, D.W.; Trifunac, A.D. Acc. Chem. Res. 1998, 31, 651
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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 NH2
.
+
[O] + +
H2 N NH2 H2 N NH2
- e- - e-
Me2N NMe2
Br2
Me2N NMe2
.
+
+ Br-
HOAc
Wurster's blue
Me2N NH2
Br2
Me2N NH2
.
+
+ Br-
HOAc
Wurster's red
227
Baeyer, A. Chem. Ber. 1875, 8, 614

Wurster, C.; Sendtner, R. Chem. Ber. 1879, 12, 1803
Wurster, C.; Schobig, E. Chem. Ber. 1879, 12, 1807
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Michaelis, L.; Schubert, M.P.; Granick, S. J. Am. Chem. Soc. 1939, 61, 1981
Ar
N N
Ar
1/2 X2 Ar
N
.
N+
Ar
X-
Ar Ar Ar Ar
Ar3 N + 1/2 Br2

.
Wieland, H. Chem. Ber. 1907, 40, 4260; 4263
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
-e -
NH .
+
-
-e
NH +2
S 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
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H2 SO4 .
+
O O
H2 SO4
O O
.
+
N N N N
O O O O
Hirschon, G.M.; Gardner, D.M.; Fraenkel, G.K. J. Am. Chem. Soc. 1953, 75, 4115
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229
Ar-NH2
SbF 5
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
- e- - e- + +
R2 N CH CH CH CH
n
n
.
+
n
NR2
S S
. N+
CH CH
. N+
. CH CH CH CH
N+ N
Hünig, S. Ann. Chem. 1964, 676, 32

Hünig, S.; Balli, H.; Conrad, H.; Schott, A. Ann. Chem. 1964, 676, 36; 52
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Hünig, S.; Geiger, H.; Kaupp, G.; Kniese, W. Ann. Chem. 1966, 697, 116
230
R1 R1
N Cl
hν
H2 SO4
. N+ H
R2 R2
Danen, W.C.; Rickard, R.C. J. Am. Chem. Soc. 1972, 94, 3254
O
O
.
_ O
.
_
+
Ph Ph
hν
.
+
+
.
+
Ph Ph Ph Ph
CN
CN CN
. . . .
A- B+ A- B+
Ph
.
+
Ph
+ A -.
Ph Ph
Ph Ph
+
Ph Ph . + A
Ph Ph
H
.
+
+ ROH
O+
R A-
. O
R
Ph Ph
Ph . Ph Ph . Ph
+ A
Neutefel, R.A.; Arnold, D.R. J. Am. Chem. Soc. 1973, 95, 4080
Pincock, J.A. Can. J. Chem. 2003, 81, 413
231
N X N X X = CR 3 , NR2 , OMe, Cl, NMe3 +

- e-
Nelsen, S.F.; Kessel, C.R.; Brien, D.J. J. Am. Chem. Soc. 1980, 102, 702
ROOC N N COOR + Ph 3 P ROOC

. N
_
N COOR
.
+ Ph 3 P+ ROOC
_
N N
COOR
ROOC
.
N
_
N COOR + Ph 3 P ROOC
. N N
COOR PPh3
+
ROOC
.
N N
COOR
+ ROOC N N COOR ROOC

PPh3
+ _
N N
COOR
+ ROOC
.
N
_
N COOR
PPh3 PPh3
+ +
ROOC N N COOR
.
+ Ph 3 P+ ROOC
.
N N
COOR
PPh3
ROOC
.
N N
COOR
+ Ph 3 P
+
ROOC N
_
N
COOR +
.
+ Ph 3 P+
PPh3 PPh3
+ +
Camp, D.; Hanson, G.R.; Jenkins, I.D. J. Org. Chem. 1995, 60, 2977
232
Br . .
+
hν H+
O
- Br . MeO
O
MeO
OH
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
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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
+
XH X = OH, NH2 , SH, Cl, Br
. Cl+
H
.
CH2
+
O
H
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 Ar
Ar hν
. +
Ar
acetone-d6
O
Ar . Ar
O
Cl Cl Cl Cl
Cl Cl Cl Cl
O O
Ar Ar
Ar
Cl
Ar Cl
O Cl
O Cl
Cl
Cl
O
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 .
+ O
O2N
- e-
O2N
- CH3 . 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
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
Tokitoh, N.; Okazaki, R. Coord. Chem. Rev. 2000, 210, 251 (silylenes, germylenes, stannylenes, plumbylenes)
950 C 2 H2 O
CaH2 + Ge CaGe GeH2
- H2 - Ca(OH)2
Royen, P.; Schwarz, R. Z. Anorg. Allgem. Chem. 1933, 211, 412 (first claim, later refuted)
237
:
_ Ge
Ge Na+ + Ph Br NaBr + Ph H +
H H
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+ X-
Et3 Si+ X- X = [B(F 5 Ph)4 ]
(Me3 Si)3 Si+ X-

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
Mes R
Mes R
Si Si
+ - + -
+ R3 Si [B(F5 Ph)4 ] Mes3 Si [B(F5 Ph)4 ] + R
Mes
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 ] Mes3 Si [HCB11 Me5 Br6 ] + Si
Mes
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
SiMe3 SiMe3
R1 + R1
R1 R1
Me3Si H+ Me3Si
+ MeOH MeO
Si R2 Si R2
- H2 O Si R2 Si R2
Me3Si Me3Si - H+
Me3Si Me3Si
SiMe3 SiMe3
SiMe3 SiMe3
Sternberg, K.; Michalik, M.; Oehme, H. J. Organometallic Chem. 1997, 533, 265
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 C R2
+ Nu
R1 R2
Nu +
O O-
S R1 S R2
+ Nu
R1 R2
Nu +
O O-
P R1 P R2
+ Nu
R1 R2
Nu +
240
Ph H Ph NHPh
N O
N H2 O
HBr
R OH + EtOH
- HBr
R OEt R NHPh
R OEt OEt
Br
O O - Na+
+ NaOEt CF3 OEt

CF3 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 NH2 OH N
HO NHOH HA
+ NH 2 OH
- H2 O
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 Ph Ph
Ph OSO2 C6H 4p-Br
C*
BF3 C* C
-
C* C pBrC6 H4 SO3 C*
Ph Ph
S+
Ph - pBrC6 H4 SO3 H S S
XC6H 4S X X
C6 H4X
242
Ph Ph Ph Ph
H2
Raney Ni C*H CH NBS C* C KMnO4
CH2 C*H2 CH C*H
Ph Ph Ph Ph
X X X X
Ph Ph
C* C
O + PhCOOH + + PhC * OOH
O
X 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

243
R1 O3SAr R1 Cl
R3
R3 -S R2 HCl S+ Cl- R3 -S R2
R2 O3SAr R2 Cl
- ArSO3 H
R1 R2
R3 -S R1 R3 -S 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 CO CO
CO CO O- Li+ CO O- Me4 N+
PhLi / Et2 O Me4 N+ Cl-
OC M CO OC M C OC M C
- LiCl
OC OC OC Ph
CO Ph
CO CO
- LiBF4
Me3 O+ BF4 -
- Me2 O - Me4 N+ X- HX
M = W, Cr, Mo
CO CO
CO OMe CO OH
CH2 N2
OC M M
OC
OC - N2
Ph OC Ph
CO CO
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
245
O - K+
C8 K R1 -COCl
M(CO)6 K2 [M(CO)5 ] (OC) 5M
O R1
R3 R2 -X
R1 N
R4 OR2
O - K+
K+ R3 (OC) 5M
_
(OC) 5M N R1
R1 R4
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 Me3CCH 2 H
M[CH2 CMe3 ]3 Cl2 + 2 LiCH2 CMe3 Me3CCH 2 M

- 2 LiCl
- CMe4 CMe3
Me3CCH 2
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 H
CH3 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 CO
CO Ph CO
OC W + BI3 I W C Ph + CO + BI2 OMe
OC
OC OMe
CO 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
[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 W PMe 3
OC 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)
Ph
N CO N CN
2. [Ph3 P-N=PPh3 ]+ X-
[Ph3 P-N=PPh3 ]+
W C Ph ( - KX) NC W
Br
N CO N 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 CH2 PF 4 -
- MeOH - AgCl
- MeOH HBF 4 CO
+ +
(Cp)(CO)2 Fe CH2 BF4 - Fe(CO)2 (Cp)
CH2 C O PF 4 -
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 PPh3
CN
_ Ir CN
+ OC
Ph3 P Ir PPh3 + K N C N C
- KCl
CN
Cl CN
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
Cl Re(CO)5
NMe2 NMe2
+ Na[Fe(CO)2 (Cp)] N+
- NaCl
Cl Fe(CO)2 (Cp)
_
NMe2 Co(CO)3
+ Na[Co(CO)4 ] N+ N+
- NaCl - CO
Cl
_
NMe2 Mo(CO) 2(Cp)
+ Na[Mo(CO)3 (Cp)] N+ N+
- NaCl - CO
Cl
King, R.B.; Hodges, K.C. J. Am. Chem. Soc. 1974, 96, 1263
251
CH3
(CO) 5Cr + Cy-NC (OC)5 Cr[Cy-N=C=C(Me)(OMe)] Cr(CO)5 + Cy-N=C=C(Me)(OMe)
OCH3
Kreiter, C.G.; Aumann, R. Chem. Ber. 1978, 111, 1223
Ph OEt Ph OEt
OEt
KMnO4 O R
R-N=C=O (CO)5W R
N N
(CO) 5W + Cy-NC W(CO)5 [Cy-N=C=C(OEt)(Ph)]
Fe(NO3 )3
N N
Ph
Cy O Cy 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
EtO Ph
H R
H
OEt
Ph (CO) 5W OEt
R H (CO) 5W
(CO) 5W
(CO) 5W + Cy-NC N C
N R
N Ph
OEt Cy Ph
Cy
Cy
Aumann, R.; Kuckert, E. Chem. Ber. 1987, 120, 1939
Transition Metal Iminium Complexes

252
R1 R3
N+
R2 M[Ln] R
4
Reviews:
None.
+
N HCl NH
HCl
Cl- NH
OC PPh2
W OC PPh2 PPh2 PPh2
P CO W
P CO W
Ph CO Cl
Ph Ph CO Cl CO
Ph 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
[Ln]M Si
Reviews:
Lickliss, P.D. Chem. Soc. Rev. 1992, 21, 271
Ogino, H. The Chemical Record 2002, 2, 291
253
NEt 2
CH3
hν
Fe(CO)5 + H Si CH3 (CO) 4Fe Si NHEt2
- CO
CH3
CH3
Schmid, G.; Welz, E. Angew. Chem. Int. Ed. 1977, 16, 785
Cl O OtBu O
Na2 Fe(CO)4 + tBuO Si Cl + (CH3) 2N P N(CH3) 2 (CO) 4Fe Si N P N(CH3) 2

- 2 NaCl OtBu N(CH3) 2
OtBu N(CH3) 2
Zybill, C.; Muller, G. Angew. Chem. Int. Ed. 1987, 26, 669
PMe 3 Ph PMe 3 Ph
CH3 CN
_ Ru+ Si OTf + NaBPh 4 _ Ru+2 Si NCCH 3 BPh4 -
- NaOTf
PMe 3 Ph PMe 3 Ph
Straus, D.A.; Tilley, T.D.; Rheingold, A.L.; Geib, S.J. J. Am. Chem. Soc. 1987, 109, 5872
254
S
PCy3 +
(CO) 4Os Si SEt
Ru+
H Pt Si BPh4 -
_
PCy3 SEt
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
hν
Fe(CO)5 + H Si NMe2 (CO) 4Fe Si NHMe2
- 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 [Ln]M M[Ln]
+ + +
[Ln]M R2
R2 R1 R1 R2
Reviews:
Chisholm, M.H.; Clark, H.C. Acc. Chem. Res. 1973, 6, 202

255
R +
R
Cl Q
Pt + + AgPF6 Q [PF 6 -]
Q Me - AgCl Pt
R Q Me
R
R
R
Q R
+
+
+ Q Me Pt
R Q
Pt
R Pt R
Q Me Q
Q Me
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

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 Cl Cp CN
+ 2 PR 3 R3 P M C + 3 CO
Cl CN
NC M(CO)3Cp PR3
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 CN
M(CO)5 -
+ Cl-
Cl CN
X CN
(CO) 3(Cp)M CN
X CN
M(Cp)(CO)3 - + Cl-
X CN
X = H, Cl, CN; M = Mo, W
King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1972, 94, 1784
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(CO)5 [=C=C=C(Ph)(NEt 2 )] + [EtOEX3 ]- H+
M = Cr, W 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)
O *3
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
+ CF3 CO2
+ -
H CF3 COO
Cl+
Cl Cl Cl
Peterson, P.E.; Duddey, J.E. J. Am. Chem. Soc. 1963, 85, 2865
CF3 CO2
H+ + CF3 CO2 -
- HOTs +
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 + X
Ph
Miller, L.L.; Kaufman, D.A. J. Am. Chem. Soc. 1968, 90, 7282
263
- OOC Ph - OOC Ph - OOC Ph

- OOC H2 O
C+ Ph
-
X -X OH O
- CO2
- CO2
Ph Ph
O
Grob, C.A. Bull. Soc. Chim. Fr. 1960, 1360
EtO O
Br 80% EtOH/H2 O
+
X
- Br- - H+
X
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
264
OSO2 CF3 OMe

+ MeOH
R2
- CF3 SO3 - - H+
R1 R2 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 Ph
KNH2 /NH3 (l)
C : Ph Ph + KBr
Ph Br Ph
Coleman, G.H.; Maxwell, R.D. J. Am. Chem. Soc. 1934, 56, 132
Emschwiller, G. Bull. Soc. Chim. Fr. 1935, 2, 1625

265
Kobrich, G. Angew. Chem. Int. Ed. 1967, 6, 41
ON R
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 OSO2 CF3 R R
+ tBuO-
H :
- CF3 SO3 - - HOtBu
R R R
tBuO-
R 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 _ PhCH=CH2
- HOtBu
: Ph
- KCl
Cl 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 Ph Ph
N N N
2 :
N N N
Ph 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 R
+
+
+ E+
H H H
E E +
E
R = EDG, ortho substitution
+ H H H
R R R R
+ E+ E E E
+ +
R = EWG, meta substitution
Reviews:
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
HBr / Al2 Br6 +
+
H+
H H
+ H H
H H R
R
+
R
H
H R +
R - H+
R
H
+ H
R
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
+ 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 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 R3
+
_
N R4
R2 R5
Reviews:
Zugravescu, I.; Petrovanu, M. N-Ylid Chemistry, (translated by C. Stoicescu) McGraw-Hill International Book Co.: New York, 1976
271
+ +
- NMe3
H NMe3 Br
_
Ag2 O
Ingold, C.K.; Jessop, A.J. J. Chem. Soc. 1929, 2357
+ +
- NMe3
H NMe3 Br
_
PhLi
- PhH
- LiBr
Wittig, G.; Felletschin, G. Ann. Chem. 1944, 555, 133
1. OH
_ +
R1 R2 R1
+ - NMe3
Me4 N X + Ph-Li Me3N+ CH2
- Ph-H 2. H2 O R2
OH-
- LiX
O
_ R1 R2
+ -
Me4 P X + Ph-Li Me3P+ CH2 + O=PMe3
- Ph-H
R1 R2
- LiX
272
+ _ R1 R2
Ph3 P-CH 3 X- + Ph-Li Ph3 P+ CH2 + O=PPh 3
- Ph-H R1 R2
- LiX
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+ Ph
: Me2N
_ Ph
∆ PhCH 2 NMe2
- N2
Bamford, W.R.; Stevens, T.S. J. Chem. Soc. 1952, 1975
Cl Cl
Cl hν Cl _
+ Et2 NH
- N2
N N
N+
Et Et
H
Bonneau, R.; Liu, M.T.H. J. Am. Chem. Soc. 1991, 113, 9872
273
West, F.G.; Glaeske, K.W.; Kevin, W.; Naidu, B.N. Synthesis 1993, 977
Ph Ph Ph
H
_
N2 hν CHCl3
N+ N+
NMe2
- N2 - : 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 Ph
N Ts hν
O+
O Ph - NaTs
- N2 n
n
Kirmse, W.; Kund, K. J. Am. Chem. Soc. 1989, 111, 1465
(iii) Phosphonium ylides
R1 R3
+
_
P R4
R2 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 Ph3 P+ COOEt
Cl-
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 Ph3 P+ COR
Cl-
R = Me, Ph
Michaelis, A.; Kohler, E. Chem. Ber. 1899, 32, 1566

Ramirez, F.; Dershowitz, S. J. Org. Chem. 1957, 22, 41
∆
Ph
+
Ph3 P + Ph 2 CN2 Ph3 P=N-N=CPh2 Ph3 P=CPh 2 _
Ph3 P
- N2
Ph
Staudinger, H.; Meyer, J. Helv. Chim. Acta 1919, 2, 635
Ph Ph
H nBuLi +
Ph3 P=CPh 2 _
Ph3 P
Ph3 P+ Ph - nBuH
- - LiBr
Br Ph
Coffmann, D.D.; Marvel, C.S. J. Am. Chem. Soc. 1929, 51, 3496
275
+ + PPh3
H PPh3 X-
_
NH 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
- H2 O
Ph O+ - N+ - N+
I Ph I - NaI Ph
_N
HN
Ph Ph
Scheider, W.; Seebach, F. Chem. Ber. 1921, 54, 2285

Scheider, W. Ann. Chem. 1924, 438, 115
276
N+ N+ Ar N+ Ar
Ar NaOH
Br- _
- H2 O
O - NaBr H O- H O
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
277
N+ -
O I
O O
H O
_ H HI
Ph H _ N+ N+
- N2 Ph Ph Ph I-
:
N2 +
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+ R2
Ph
Ph
R1 = H, Ph; R2 = H, Me
Duerr, H.; Heu, B.; Ruge, B.; Scheppers, G. Chem. Commun. 1972, 1257
278
(v) Sulfimine ylides
R2
_
R1 N S+
R3
Reviews:
None.
Et
_
SO2 NH2 + Et2 S SO2 N S+
Et
Mann, F.; Pope, W.J. J. Chem. Soc. 1922, 121, 1052 (first sulfimine)
O R
_
SO2 NH2 + S SO2 N S+
- H2 O
R R R
Tarbell, D.S.; Weaver, C. J. Am. Chem. Soc. 1941, 63, 2939
(vi) Sulfonium ylides
R1 R3
+
_ S
R2 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
S+
_
Ingold, C.K.; Jessop, J.A. J. Chem. Soc. 1930, 713
SH
HN NH2 NH2
O O HN NH2
O HN NH2 O
_ H S+ N S
Ph H Ph _ H S
- N2 Ph
Ph
:
N2 + H - H2 O
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
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
Np
(CH3 )2 C=O
_ O+
H
Np
CH3 CN
N2 _ N+
:
hν
H
Np H
Np H - N2 Np
N _ N+
Np
Et3 N +
_ NEt 3
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
281
N
N N hν tBu
:
_ N+
- N2 tBu Cl
tBu Cl
Cl
Jackson, J.E.; Soundarajan, N.; Platz, M.S.; Liu, M.T.H. J. Am. Chem. Soc. 1988, 110, 5595
R1
N
N hν
: R1 -S-R2
_ S+
R2
- N2
Ph R1
N N
:
hν R1 -S-R2
_ S+
- N2 Ph H
Ph 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
hν
Ph OH PhCH C O
- CO
Ph 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)........................................................................................... 1

N-Acylonium ions (acylammonium ions).................................................................................... 2
Alleneoxide...................................................................................................................... 2
Aromatic pi-complexes......................................................................................................... 3
Charge transfer complexes............................................................................................ 4
Sandwich complexes (metallocenes)................................................................................. 7
Aromatic sigma complexes (see Meisenheimer-Jackson, Janovsky, Wheland)......................................... 8
Arylium ions (see phenyl cation).............................................................................................. 10
Aziridinium ions................................................................................................................. 10
Benzyne (arynes)................................................................................................................ 11
Betaines (phosphonium betaines)............................................................................................. 18
Biradicals......................................................................................................................... 18
Thiele hydrocarbon..................................................................................................... 19
Chichibabin hydrocarbon............................................................................................. 19
Schlenk-Brauns hydrocarbon........................................................................................ 20
Müller hydrocarbon................................................................................................... 21
Norrish Type I......................................................................................................... 23
Norrish Type II........................................................................................................ 23
Bridged carbocations (see halonium, non-classical, phenonium)......................................................... 25
Carbanions....................................................................................................................... 25
Carbanions via E1cb............................................................................................................ 27
Carbenes (methylenes)......................................................................................................... 28
Carbenes (singlet)............................................................................................................... 34
Carbenes (triplet)................................................................................................................ 35
Carbenes (Arduengo)........................................................................................................... 36
Carbenes (Bertrand)............................................................................................................ 36
Dicarbenes....................................................................................................................... 37
Carbocations..................................................................................................................... 37
Carbynes......................................................................................................................... 43
2,4- and 2,5-Cyclohexadienones.............................................................................................. 44
2,4- and 2,5-Cyclohexadienimines............................................................................................ 44
Cyclopropenyl cations.......................................................................................................... 46
Dications.......................................................................................................................... 47
Benzidine rearrangement............................................................................................... 47
Dications synthesized in magic acid.................................................................................. 47
Violenes.................................................................................................................. 48
Wallach intermediate.................................................................................................... 49
284
Wurster salts............................................................................................................. 49
1,3-Dioxolenium ions........................................................................................................... 50
1,3-Dipoles (carbene traps)..................................................................................................... 52
Azomethine ylide........................................................................................................ 52
Carbonyl oxide (Criegee zwitterion).................................................................................. 52
Carbonyl ylide........................................................................................................... 52
Nitrile ylide.............................................................................................................. 57
Thiocarbonyl ylide...................................................................................................... 58
1,3-Dipoles (nitrene traps)...................................................................................................... 59
Azomethines............................................................................................................. 59
Azonium imines......................................................................................................... 60
Carbonyl imines......................................................................................................... 61
Nitrilimines.............................................................................................................. 61
Nitrosoimines............................................................................................................ 62
Thiocarbonyl imines.................................................................................................... 62
Doering-Zeiss intermediate...................................................................................................... 62
Enols and enolates............................................................................................................... 63
Episulfonium ions................................................................................................................ 65
Sulfenium ions.......................................................................................................... 65
Sulfonium ions.......................................................................................................... 69
Extended cumulenones.......................................................................................................... 71
Propadienones (methyleneketenes)................................................................................... 71
Butatrienones............................................................................................................ 78
Iminopropadienones.................................................................................................... 80
Halonium ions.................................................................................................................... 82
Hydronium ions.................................................................................................................. 85
Iminium ions...................................................................................................................... 85
Janovsky complex............................................................................................................... 86
Ketenes............................................................................................................................ 86
Metal ketenides.......................................................................................................... 89
Ketene zwitterions............................................................................................................... 90
Ketyl radicals and ketyl radical ions........................................................................................... 91
Meisenheimer-Jackson complexes............................................................................................. 95
Mercurinium ions................................................................................................................ 96
Metal carbenoids................................................................................................................. 100
Nicholas cation................................................................................................................... 102
Nitrenes........................................................................................................................... 103
Dinitrenes................................................................................................................ 105
Trinitrenes................................................................................................................ 106
285
Nitrenium ions.................................................................................................................... 107

Nitrilium ions..................................................................................................................... 110
Nitronium ions................................................................................................................... 110
Nitrosonium ions................................................................................................................. 111
Non-classical ions (hyperco-ordinate carbocations, sigma-bridged cations).............................................. 112
Oxenium ions..................................................................................................................... 114
Oxirene............................................................................................................................ 117
Oxonium ions..................................................................................................................... 121
Acetoxonium ions....................................................................................................... 121
Flavinium ions........................................................................................................... 122
Flavylium salts.......................................................................................................... 122
Meerwein salts........................................................................................................... 123
Methoxonium ions...................................................................................................... 124
Pyrylium salts........................................................................................................... 124
Phenonium ions.................................................................................................................. 125
Phenyl cation (phenylium ion, arylium ion, benzene cation)............................................................... 126
Phosphenium ions............................................................................................................... 128
Phosphonium ions............................................................................................................... 129
o-Quinodimethanes (o-xylylenes).............................................................................................. 131
p-Quinodimethanes (p-xylylenes).............................................................................................. 132
o-Quinonemethides and p-Quinonemethides.................................................................................. 133
Radicals........................................................................................................................... 134
Carbon centred.......................................................................................................... 136
Gomberg radical................................................................................................ 136
Alkyl radicals................................................................................................... 137
Aryl radical (phenyl radical).................................................................................. 142
Benzoyl radical................................................................................................. 150
Acyl radicals.................................................................................................... 154
Benzyl radical................................................................................................... 158
Koelsch radical................................................................................................. 160
Group IV (Si, Ge, Sn)................................................................................................. 160
Silyl.............................................................................................................. 160
Germyl.......................................................................................................... 163
Stannyl.......................................................................................................... 164
Group V (N, P)......................................................................................................... 166
Aminyl........................................................................................................... 166
N-Alkoxy-N-alkylamino radicals............................................................................ 169
Amido radicals.................................................................................................. 170
Hydrazyl........................................................................................................ 171
286
Nitroxide radicals.............................................................................................. 174

Thioaminyl radicals............................................................................................ 175
Sulfonamidyl radicals.......................................................................................... 176
N-Thiosulfonamidyl radicals................................................................................. 178
Verdazyls........................................................................................................ 179
Phosphinoyl radicals........................................................................................... 182
Phosphinyl radicals............................................................................................ 187
Phosphoranyl radicals......................................................................................... 191
Thiophosphinoyl (phosphinothioyl) radicals............................................................... 193
Group VI (O, S, Se).................................................................................................... 194
Acetoxy (acetoxyl) radicals................................................................................... 194
Alkoxy radicals................................................................................................. 196
Iminoxyl radicals............................................................................................... 198
Nitroxyl radicals................................................................................................ 200
Kenyon-Banfield radical...................................................................................... 205
Peroxy radicals................................................................................................. 206
Phenoxy (phenoxyl) radicals................................................................................. 207
Sulfanyl (mercapto, thiyl) radicals........................................................................... 213
Sulfinyl radicals................................................................................................ 214
Sulfonyl radicals............................................................................................... 216
Sulfuranyl radicals............................................................................................. 217
Thionitroxide radicals.......................................................................................... 219
Thiophenoxy (phenylthio, phenylthiyl, benzenethiyl) radicals........................................... 221
Phenylselanyl radical.......................................................................................... 222
Selanyl........................................................................................................... 223
Radical anions.................................................................................................................... 223
Radical cations.................................................................................................................... 225
Wurster salts............................................................................................................. 226
Distonic................................................................................................................... 232
Silylenes and germylenes....................................................................................................... 235
Silylium ions (silylenium ions, silicenium ions, silyl cations, silicocations)............................................. 237
Tetrahedral intermediates........................................................................................................ 239
Thiirenium ions................................................................................................................... 241
Transition metal carbene complexes........................................................................................... 243
Transition metal carbyne complexes........................................................................................... 246
Transition metal ketenyl complexes............................................................................................ 247
Transition metal keteniminium complexes.................................................................................... 249
Transition metal iminium complexes........................................................................................... 251
Transition metal silene complexes.............................................................................................. 252
287
Transition metal vinyl cation complexes....................................................................................... 254

Transition metal vinylidene complexes........................................................................................ 255
Transition metal vinylidenecarbene complexes............................................................................... 257
Triplet ketones (excited state)................................................................................................... 258
Triplet olefins (excited state).................................................................................................... 259
Tropylium ion.................................................................................................................... 259
Vinyl cations...................................................................................................................... 261
Vinylidenes (methylene carbenes, alkylidene carbenes)..................................................................... 264
Vinylidenecarbenes (allenylidenes, alkenylidene carbenes)................................................................. 265
Wallach intermediate (see Dications)........................................................................................... 266
Wanzlich carbenes............................................................................................................... 266
Wheland intermediates (arenium ions, benzenium ions).................................................................... 267
Ylides (1,2-dipoles).............................................................................................................. 270
Ammonium ylides....................................................................................................... 270
Oxonium ylides.......................................................................................................... 273
Phosphonium ylides.................................................................................................... 273
Pyridine ylides........................................................................................................... 275
Sulfimine ylides......................................................................................................... 278
Sulfonium ylides........................................................................................................ 278
Trapping of carbenes generated by flash photolysis................................................................ 279
Ynols (hydroxyacetylenes)...................................................................................................... 281

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1

Reaction Intermediates in Organic Chemistry: the "Big Picture"

Acylium ions (oxocarbonium ions)

N-Acylonium ions (acylammonium ions)

Kröhnke, F.; Heffe, W. Chem. Ber. 1937, 70B, 1720

(i) Charge transfer complexes

Dewar, M.J.S. Nature 1945, 156, 784 (first suggestion)

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

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

Reeves, L.W.; Schneider, W.G. Can. J. Chem. 1957, 35, 251

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

(ii) "Sandwich" complexes (metallocenes)

Hein, F. Chem. Ber. 1919, 52, 195

Kealy, T.J.; Pauson, P.L. Nature 1951, 168, 1039

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

Reaction with electrophiles, E+

Reaction with nucleophiles, Nu-

Arylium ions (see phenyl cation)

Berthelot, A. Compt. Rend. 1866, 63, 790

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

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

Haeussermann, C. Chem. Ber. 1900, 33, 939

KOH / EtOH EtOH

Meyer, K.H.; Bergius, F. Chem. Ber. 1914, 47, 3159

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

Wittig, G. Naturwiss. 1942, 30, 696

Ph-Li COOH (Ph)

Huisgen, R.; Rist, H. Naturwiss. 1954, 41, 358

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

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

Betaines (phosphonium betaines)

Thiele hydrocarbon (biradical)

Thiele, J.; Balhorn, H. Chem. Ber. 1904, 37, 1463

Chichibabin hydrocarbon (biradical)

Chichibabin, A.E. Zh. Russ. Fiz.-Khim., Obshchestva 1907, 39, 925

Schlenk-Brauns hydrocarbon (biradical)

Müller hydrocarbon (biradical)

Müller, E.; Neuhoff, H. Chem. Ber. 1939, 72, 2063

Müller, E.; Pfanz, H. Chem. Ber. 1941, 74, 1051

Wittig, G.; von Lupin, F. Chem. Ber. 1928, 61B, 1627

Müller, E.; Dammerau, I. Chem. Ber. 1937, 70B, 2561

Bamford, C.H.; Norrish, R.G.W. J. Chem. Soc. 1935, 1504

Harder, S. Chem. Eur. J. 2002, 8, 3229

Zincke, T.; Suhl, R.S. Chem. Ber. 1907, 39, 4148

Schlenk, W. Ann. Chem. 1910, 372, 1

Wren, H. J. Chem. Soc. 1910, 95, 1583

Curtius, T. Chem. Ztg. 1912, 35, 249

Carbanions via E1cb (elimination unimolecular carbanion) mechanism

Hughes, E.D.; Ingold, C.K. J. Chem. Soc. 1933, 523

Carbenes or methylenes (general)

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

CHCl3 + OH- H2 O + CCl3 -

CCl3 - :CCl2 + Cl-

Hine, J. J. Am. Chem. Soc. 1950, 72, 2438 (haloform hydrolysis)

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

Herzberg, G.; Shoosmith, J. Nature 1959, 183, 1801

Herzberg, G. Proc. Roy. Soc. London 1961, 262A, 291

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