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Abstract

Data on the influence of neutral salts on the rates of unimolecular heterolyses of organic substrates, obtained mainly by the verdazyl method, are summarized here. It is assumed that heterolysis takes place with consecutive formation of four ion pairs: contact (CIP), cavity-separated (CSIP), one solvent moleculeseparated (SIP) and solvent-separated (SSIP). $RX ⇄ \underset{CIP}{R^{+} X^{-}} \overset{O}{\underset{\leftarrow}{\to}} \underset{CSIP}{R^{+} | O | X^{-}} ⇄ \underset{SIP}{R^{+} {|Solv|X}^{-}} ⇄ \underset{SSIP}{R^{+} | Solv,Solv | X^{-}} \to Products$

In the limiting step, the CIP interacts with a solvent cavity and the CSIP is formed, which converts quickly into the SIP and subsequently to the SSIP, which also quickly gives the reaction products. In the transition state, bonds between the molecules solvating the CIP are broken. In the absence of salt, the return from external ion pairs does not have much importance. The verdazyl indicator quickly and quantitatively reacts with the SSIP.

The normal salt effect takes place due to the action of salt on the covalent substrate, which catalyses CIP formation. The special salt effect is caused by the association of the salt with the CIP, which prolongs the lifetime of the intermediate and increases the probability of its contact with a solvent cavity.

The negative special salt effect is caused by association of the salt with the SIP or SSIP, which prolongs the lifetime of the intermediates and increases the probability of their contact with a solvent cavity to return to the covalent substrate. When the salt reacts with the SIP, the salt effect does not depend on the concentration and nature of verdazyl, but such a dependence takes place when the salt reacts with the SSIP.

The site of the action of the salt is determined by the Hard and Soft Acids and Bases (HSAB) principle.

Keywords

reaction mechanism heterolysis solvolysis salt effects verdazyl method ion pairs

References

Ingold

C. K.

Structure and Mechanism in Organic Chemistry, 2nd edn. Cornell University Press, New York, 1969, Chapt. VII.

Hammett

L. P.

Physical Organic Chemistry, 2nd edn. McGraw-Hill, New York, 1970, Chap. 6.9.

Raber

D. J.

, Harris

J. M.

, and Schleyer

P.v.R.

In: Ions and Ion Pairs in Organic Reactions, vol. 2. Szwarc

(ed.). Wiley, New York, 1974, pp. 247–374.

(a) Katritzky

A. R.

, and Brycki

B. E.

Chem. Soc. Rev., 1990, 19, 83–105; (b) Katritzky, A. R., Fara, D. C., Yang, H., Tämm, K., Tamm, T. and Karelson, M. Chem. Rev., 2004, 104, 175-198; (c) Streitwieser, S. Solvolytic Displacement Reactions, McGraw-Hill, New York, 1962.

Harris

J. M.

Prog. Phys. Org. Chem., 1974, 11, 89–173.

Loupy

, and Tchoubar

Effets de Sels en Chimie Organique et Organométallique. Bordas, Paris, 1988.

Dvorko

G. F.

, and Ponomarev

N. E.

Zh. Obsch. Khim., 1997, 67, 908–921.

Dvorko

G. F.

, Ponomareva

E. A.

, and Ponomarev

N. E.

Zh. Obsch. Khim., 2006, 76, 1426–1444.

Dvorko

G. F.

, and Ponomareva

E. A.

Russ. J. Org. Chem., 1998, 34, 487–501.

10.

Toteva

M. M.

, and Richard

J. P.

J. Am. Chem. Soc., 1996, 118, 11434–11445.

11.

Manege

L. C.

, Ueda

, Hojo

, and Fujo

J. Chem. Soc., Perkin Trans. 2, 1998, 1961–1963.

12.

Coxon

J. M.

Advances in Carbocation Chemistry, Vol. 2. JAI, Greenwich, 1995.

13.

Hammett

L. P.

Physical Organic Chemistry, McGraw-Hill, New York, 1940.

14.

Winstein

, Clippinger

, Fainberg

, and Robinson

G. C.

J. Am. Chem. Soc., 1954, 76, 2597–2598.

15.

Winstein

, Appel

, Baker

, and Diaz

Chem. Soc. Spec. Publ., 1965, 109–130.

16.

Huang

, Tanaka

K. S. E.

, and Bennet

A. J.

J. Am. Chem. Soc., 1998, 120, 1405–1409.

17.

Maskill

The Physical Basis of Organic Chemistry. Oxford University Press, New York, 1993.

18.

Isaacs

N. S.

Physical Organic Chemistry, 2nd edn. Wiley, New York, 1992.

19.

Gordon

J. E.

The Organic Chemistry of Electrolyte Solutions, Wiley, New York, 1975, chap. 3.

20.

Dvorko

G. F.

, Ponomarev

N. E.

, and Ponomareva

E. A.

Zh. Obsch. Khim., 1999, 69, 1835–1851.

21.

(a) Dvorko

G. F.

, Ponomareva

E. A.

, and Ponomarev

M. E.

J. Phys. Org. Chem., 2004, 17, 825–836. DOI. 10.1002/poc.757; (b) McManus, S. P., Somani, S., Harris, J. M. and McGill, R. A. J. Org. Chem., 2004, 69, 8865-8873.

22.

Frcasin

, Jähme

, Rüchardt

Ch.

J. Am. Chem. Soc., 1985, 107, 5717–5722.

23.

Ponomarev

N. E.

, Zalizny

V. V.

, and Dvorko

G. F.

Zh. Obsch. Khim. in press.

24.

Kevill

D. N.

, and D'Souza

M. Y.

J. Phys. Org. Chem., 1992, 5, 287–294.

25.

Bentley

T. W.

, and Llewellyn

Prog. Phys. Org. Chem., 1990, 17, 121–158.

26.

Dvorko

G. F.

, and Ponomareva

E. A.

Russ. Chem. Rev., 1991, 60, 2089–2112.

27.

(a) Richard

J. P.

, Toteva

M. M.

, and Amyes

T. L.

Org. Lett., 2001, 3, 2225–2228; (b) Richard, J. P. and Jencks, W. P. J. Am. Chem. Soc., 1984, 106, 1373-1383; (c) Katrizky, A. R. and Brycki, B. E. J. Am. Chem. Soc., 1986, 108, 7295-7299.

28.

Abboud

J.-L.M.

, Alkorta

, Davalos

J. Z.

, Muller

, Quintanilla

, and Rossier

J.-C.

J. Org. Chem., 2003, 68, 3786–3796.

29.

Takeuchi

, Takasuka

, Shiba

, Kinoshira

, Okazaki

, Abboud

J.-L. M.

, Notario

, and Castano

J. Am. Chem. Soc., 2000, 122, 7351–7357.

30.

Ward

A. M.

J. Chem. Soc., Part I. 1927, 445, 2285.

31.

Rudakov

E. S.

Dokl. AN SSSR., 1959, 127, 1058–1061.

32.

Oliver

S. C. G.

, and Weber

A. Ph.

Rec. Trav. Chim., 1934, 53, 869–890.

33.

Duunstee

E. F. G.

, Grunwald

, and Kaplan

M. L.

J. Am. Chem. Soc., 1960, 82, 5654–5660.

34.

Benfey

O. T.

, Hughes

E. D.

, and Ingold

C. K.

J. Chem. Soc., 1952, 2494–2498.

35.

Dvorko

G. F.

, and Ponomarev

N. E.

Zh. Obsch. Khim., 1993, 63, 565–574.

36.

Tarassenko

P. V.

, Ponomareva

E. A.

, Dvorko

G. F.

, and Babin

E. P.

Org. React. (Tartu), 1976, 13, 5–21.

37.

Tarassenko

P. V.

, Sumlivenko

N. V.

, Ponomareva

E. A.

, and Dvorko

G. F.

Zh. Obsch. Khim., 1986, 56, 447–451.

38.

Ponomarev

N. E.

, Stambirsky

M. V.

, and Dvorko

G. F.

Dopov. Akad. Nauk Ukraine, 1997, (6), 254–258.

39.

(a) Vitullo

V. P.

, and Grossman

N. P.

J. Org. Chem., 1973, 38, 179–180; (b) Vitullo, V. P. and Capp, R. J. Chem. Commun., 1978, 98-99; (c) Mease, A. D., Strauss, M. J., Horman, J., Andrews, L. J. and Keefer, R. M. J. Am. Chem. Soc 1968, 90, 1797-1801; (d) Brown, H. C. and Bell, H. M. J. Org. Chem., 1962, 27, 1928-1929; (e) Ponomarev, N. E., Stambirsky, M. V. and Dvorko, G. F. Zh. Obsch. Khim., 2005, 75, 937-944.

40.

McManus

S. P.

, and Zutaut

S. E.

Tetrahedron Lett., 1984, 25, 2859–2862.

41.

Winstein

, and Gall

J. S.

Tetrahedron Lett., 1960, 1, 31–35.

42.

Ritchie

C. D.

Acc. Chem. Res., 1972, 5, 348–354.

43.

Bentley

T. W.

, and Schleyer

P.v.R.

Adv. Phys. Org. Chem., 1977, 14, 18–67.

44.

Gumashi

, Gamba

, and Simonetta

J. Chem. Soc. Perkin Trans., 2, 1977, 162–171.

45.

(a) Salem

Electrons in Chemical Reactions, Wiley, New York, 1962, p. 58; (b) Jorgensen, W. L., Buckner, J. K., Huston, S. E. and Rossky, P. J. J. Am. Chem. Soc., 1987, 109, 1891-1899.

46.

Winstein

, and Robinson

G. C.

J. Am. Chem. Soc., 1958, 80, 169–181.

47.

Ponomareva

E. A.

, Pervishko

T. L.

, and Dvorko

G. F.

Org. React. (Tartu), 1981, 18, 312–322.

48.

Dvorko

G. F.

, Ponomareva

E. A.

, and Pervishko

T. L.

Org. React. (Tartu), 1979, 16, 298–326.

49.

Vitullo

V. P.

, and Wilgis

F. R.

J. Am. Chem. Soc., 1981, 103, 880–883.

50.

Allen

A. D.

, Fujio

, Tee

O. S.

, Tidwell

T. T.

, Tsuji

, Tsuno

, and Yatsugi

J. Am. Chem. Soc., 1995, 117, 8974–8981.

51.

Allen

A. D.

, Tidwell

T. T.

, and Tee

O. S.

J. Am. Chem. Soc., 1993, 115, 10091–10096.

52.

Ponomarev

N. E.

, and Dvorko

G. F.

Zh. Obsch. Khim., 1991, 61, 428–441.

53.

Dvorko

G. F.

, Fefer

Y. I.

, and Zhovtyak

V. N.

Zh. Obsch. Khim., 1992, 62, 639–648.

54.

Ponomareva

E. A.

, Pervishko

T. L.

, Dvorko

G. F.

, and Vasylkevych

A. I.

Org. React. (Tartu), 1984, 21, 78–83.

55.

Kinoshita

, Shibayama

, Ikai

, and Okamoto

Bull. Chem. Soc. Jpn., 1988, 61, 2817–2822.

56.

Richard

J. P.

, and Yeary

P. E.

J. Am. Chem. Soc., 1993, 115, 1739–1744.

57.

Ponomarev

N. E.

, Stambirsky

M. V.

, and Dvorko

G. F.

Zh. Obsch. Khim., 1998, 68, 106–115.

58.

Ponomarev

N. E.

, Stambirsky

M. V.

, and Dvorko

G. F.

Zh. Obsch. Khim., 2002, 72, 72–86.

59.

Savelova

V. A.

, Taran

N. A.

, and Drizhd

L. P.

Russ. J. Org. Chem., 1992, 28, 2516–2522.

60.

Dvorko

G. F.

, and Cherevach

T. V.

Zh. Obsch. Khim., 1990, 60, 2151–2160.

61.

Ponomarev

N. E.

, and Yakhimovich

R. I.

Dopov. Akad. Nauk Ukr. RSR, ser. B., 1989, (5), 45–49.

62.

Diaz

A. F.

, and Assamunt

Tetrahedron, 1974, 30, 797–800.

63.

Nasnovi

J. M.

, and Kochi

J. K.

J. Am. Chem. Soc., 1985, 107, 7880–7886.

64.

Yabe

, and Kochi

J. K.

J. Am. Chem. Soc., 1992, 114, 4491–4500.

65.

Ponomareva

E. A.

, Pervishko

T. L.

, and Dvorko

G. F.

Org. React. (Tartu), 1982, 19, 18–32.

66.

Dvorko

G. F.

, and Cherevach

T. V.

Zh. Obsch. Khim., 1990, 60, 2151–2160.

67.

Smith

W. B.

, and Bronum

G. D.

Tetrahedron Lett., 1981, 22, 2055–2058.

68.

Buncel

, Menon

, and Colpa

Can. J. Chem., 1979, 57, 999–1008.

69.

Perrin

Ch. L.

, and Pressing

J. Am. Chem. Soc., 1971, 93, 5705–5710.

70.

Ponomareva

E. A.

, Tarassenko

P. V.

, Yurchenko

A. G.

, and Dvorko

G. F.

Russ. J. Org. Chem., 1983, 19, 548–561.

71.

(a) Giddings

W. P.

, and Buchholz

P. F.

J. Am. Chem. Soc., 1964, 86, 1261–1263; (b) Bunton, C. A., Pesco, T. W., Dunlop, A. M. and Yang. K. U. J. Org. Chem., 1971, 36, 887-897.

72.

Winstein

, Smith

, and Darwish

J. Am. Chem. Soc., 1959, 81, 511–512.

73.

Benfey

O. T.

, Hughes

E. D.

, and Ingold

C. K.

J. Chem. Soc., 1952, 2488–2493.

74.

Sneen

R. A.

Acct. Chem. Res., 1973, 6, 46–53.

75.

Bensley

, and Kohnstam

J. Chem. Soc., 1955, 3407–3416.

76.

Vitullo

V. P.

, and Wilgis

F. R.

J. Am. Chem. Soc., 1981, 103, 1982–1984.

77.

Rappoport

, Ben-Yacov

, and Kaspi

J. Org. Chem., 1978, 43, 3678–3684.

78.

Song

B. D.

, and Jencks

W. P.

J. Am. Chem. Soc., 1987, 109, 3160–3163.

79.

Anantaraman

, and Muraleedharan Pillai

Indian J. Chem. 1976, 14B, 129.

80.

Nair

M. R.

, and Shaji

V. R.

Indian J. Chem. 1988, 27A, 242–243.

81.

Anantaraman

, and Ramaswami Iver

Indian J. Chem. 1976, 14A, 532–533.

82.

Dvorko

G. F.

, and Cherevach

T. V.

Zh. Obsch. Khim., 1991, 61, 415–425.

83.

Ponomareva

E. A.

, Tarassenko

P. V.

, Yurchenko

A. G.

, and Dvorko

G. F.

Russ. J. Org. Chem., 1983, 19, 2503–2516.

84.

Dvorko

G. F.

, Ponomareva

E. A.

, and Yavorskaya

I. F.

Russ. J. Org. Chem., 1990, 26, 598–609.

85.

Ponomareva

E. A.

, Yavorskaya

I. F.

, and Dvorko

G. F.

Russ. J. Org. Chem., 1990, 26, 578–589.

86.

Winstein

, Clippinger

, Fainberg

A. H.

, Heck

, and Robinson

G. C.

J. Am. Chem. Soc., 1956, 78, 328–325.

87.

Dvorko

G. F.

, and Cherevach

T. V.

Zh. Obsch. Khim., 1988, 58, 1371–1383.

88.

Bataille

, and Landais

C. R. 1973, 276, 1307–1310.

89.

Pervishko

T. L.

, Ponomareva

E. A.

, and Dvorko

G. F.

Org. React. (Tartu), 1990, 27, 35–43.

90.

Vitullo

V. P.

, and Wilgis

F. R.

J. Am. Chem. Soc., 1981, 103, 880–883.

91.

Dvorko

G. F.

, and Fefer

Y. I.

Dokl. Acad. Nauk SSSR., 1990, 312, 111–117.

92.

Kaatre

, Pottal

, and Schumacher

J. Phys. Chem., 1992, 96, 6017–6021.

93.

Richard

J. P.

, and Tsuji

J. Am. Chem. Soc., 2000, 122, 6553–6559.

94.

Song

B. D.

, and Jencks

W. P.

J. Am. Chem. Soc., 1989, 111, 8470–8479.

95.

McClelland

R. A.

, Cozens

F. L.

, Steenken

, Amyes

T. L.

, and Richard

J. P.

J. Chem. Soc., Perkin Trans. 2, 1993, 1717–1722.

96.

McClelland

R. A.

, Kanagasabapathy

V. M.

, and Steenken

J. Am. Chem. Soc., 1988, 110, 6913–6914.

97.

Dvorko

G. F.

, and Yevtushenko

N. Y.

Dopov. Akad. Nauk Ukr. RSR, ser. B., 1990 (6), 46–48.

98.

Ponomareva

E. A.

, Yavorskaya

I. F.

, and Dvorko

G. F.

Russ. J. Org. Chem., 1990, 26, 540–548.

99.

Polumbrik

O. M.

Chemistry of Verdazyl Radicals. (Russ.) Naukova Dumka: Kiev, 1984, 98.

100.

Polumbrik

O. M.

, Dvorko

G. F.

, and Vasylkevych

N. G.

Theor. Exp. Khim., 1973, 9, 37–42.

101.

Bagillo

V. I.

, Atamanyuk

V. Y.

, and Gragerov

I. P.

Theor. Exp. Khim., 1984, 20, 235–238.

102.

Bagillo

V. I.

, Atamanyuk

V. Y.

, Levit

A. F.

, and Gragerov

I. P.

Theor. Exp. Khim., 1983, 19, 225–230.

103.

Dvorko

G. F.

, Vasylkevych

A. I.

, and Ponomareva

E. A.

Russ. J. Org. Chem., 1991, 27, 1928–1936.

104.

Dvorko

G. F.

, Golovko

N. N.

, and Ponomareva

E. A.

Zh. Obsch. Khim., 1996, 66, 1334–1340.

105.

Dvorko

G. F.

, Golovko

N. N.

, and Ponomareva

E. A.

Zh. Obsch. Khim., 1996, 66, 1506–1513.

106.

Mohammad

, and Kosower

E. M.

J. Am. Chem. Soc., 1971, 93, 2713–2719.

107.

Lund

, and Lund

Acta Chem. Scand., 1986, B 40, 470–485.

108.

Dvorko

G. F.

, and Yevtushenko

N. Y.

Zh. Obsch. Khim., 1991, 61, 2051–2059.

109.

Dvorko

G. F.

, and Yevtushenko

N. Y.

Zh. Obsch. Khim., 1991, 61, 2059–2067.

110.

Dvorko

G. F.

, and Cherevach

T. V.

Zh. Obsch. Khim., 1991, 61, 2067–2072.

111.

Dvorko

G. F.

, and Zhovtyak

V. N.

Zh. Obsch. Khim., 1990, 60, 880–891.

112.

Jackson

, and Kohnstam

Chem. Commun., 1965, (13), 279–280.

113.

(a) Lucas

G. R.

, and Hammett

L. P.

J. Am. Chem. Soc., 1942, 64, 1928–1936; (b) Richard, J. P. J. Org. Chem., 1992, 57, 625-629; (c) Richard, J. P. J. Am. Chem. Soc., 1989, 111, 1455-1465; (d) Richard, J. P. and Yeary, P. E. J. Am. Chem. Soc., 1993, 115, 1739-1744; (e) Manege, L. C., Ueda, T., Hojo, M. and Fujio, M. J. Chem. Soc., Perkin Trans., 2, 1998, 1961-1965.

114.

Dvorko

G. F.

, Golovko

N. N.

, Pervishko

T. L.

, and Ponomareva

E. A.

Dokl. Acad. Nauk RF., 1994, 334, 60–63.

115.

Dvorko

G. F.

, Golovko

N. N.

, Pervishko

T. L.

, and Ponomareva

E. A.

Zh. Obsch. Khim., 1994, 64, 1281–1292.

116.

Dvorko

G. F.

, Pervishko

T. L.

, Leunov

D. I.

, and Ponomareva

E. A.

Russ. J. Org. Chem., 1997, 33, 565–573.

117.

Sannigrahi

A. B.

Chem. Educ., 1986, 63, 843–844.

118.

Salomon

, and Plichta

E. J.

Electrochim. Acta, 1984, 29, 731–735.

119.

Dvorko

G. F.

, Ponomareva

E. A.

, Golovko

N. N.

, and Pervishko

T. L.

Zh. Obsch. Khim., 2005, 75, 105–110.

120.

Pervishko

T. L.

, Koshchiy

I. V.

, Leunov

D. I.

, and Dvorko

G. F.

Dopov. Akad. Nauk Ukraine, 1995, (3), 86–89.

121.

Dvorko

G. F.

, and Ponomareva

E. A.

Dokl. Acad. Nauk SSSR., 1990, 315, 877–880.

122.

Pearson

Coord. Chem. Rev., 1990, 100, 403–423.

123.

Gajewski

J. J.

J. Am. Chem. Soc., 2001, 123, 10877–10883.

124.

Ülrich

Chem. Zeit., 1984, 108, 381–396.

125.

Anteunis

, and Peeters

H. L.

J. Org. Chem., 1975, 40, 307–311.

126.

Kinoshita

, Shibayama

, Ikai

, and Okamoto

Bull. Chem. Soc. Jpn., 1988, 61, 2917–2922.

127.

Dvorko

G. F.

Dopov. Akad. Nauk Ukraine, 1996, (4), 109–114.

128.

Sneen

R. A.

, and Larsen

J. W.

J. Am. Chem. Soc., 1969, 91, 362–369.

129.

Shiner

V. J.

, Fisher

R. D.

, and Dowd

J. Am. Chem. Soc., 1969, 91, 7748–7756.

130.

Cramer

J. A.

, and Jewet

J. G.

J. Am. Chem. Soc., 1972, 94, 1377–1381.

131.

Panchenko

B. V.

, and Gershikov

A. G.

Theor. Exp. Khim., 1987, 23, 91–94.

132.

McLennan

D. J.

, and Martin

P. L.

J. Chem. Soc., Perkin Trans. 2, 1982, 1091–1095.

133.

Shakhparonov

M. I.

Mechanisms of Rapid Processes in Liquids. (Russ.) Vysshaya Shkola: Moscow, 1980, p. 111.

134.

Goering

H. L.

, and Hopf

J. Am. Chem. Soc., 1971, 93, 1224–1229.

135.

Raber

D. J.

, Harris

J. M.

, and Schleyer

P.v.R.

J. Am. Chem. Soc., 1971, 93, 4824–4831.

136.

Kinoshita

, Keizo

, Kashimura

, Fujiwara

, and Okamoto

Bull. Chem. Soc. Jpn., 1986, 59, 2843–2852.

Nature of Salt Effects and Mechanism of Covalent Bond Heterolysis

Abstract

Keywords

References