Patai S., Rappoport Z. 1997 The chemistry of functional groups. The chemistry of double-bonded functional groups / 1355 149

A very important ion related to thiocarbonyl compounds is the 1,3-dithiole-2-thione-4,5- dithiolate (isotrithione-dithiolate, dmit) (159), introduced by Steimecke and coworkers681 in 1975. It is formed as the main product by chemical (with sodium or potassium)681,682 or electrochemical reduction683 of CS2 in DMF (reaction 166).

Nowadays, transition metal chelates of dmit are studied worldwide by numerous research groups. This is stimulated by those properties of the dmit chelates which favor electrical conductivity in molecular metals, e.g. planarity with delocalized -electrons as well as open-shell character (dithiolene behavior)29.

The first molecular inorganic superconductor, [TTF][Ni(dmit)2]2 (TTF D tetrathiafulvalene), was obtained in 1986 by Cassoux and collaborators24,684 686.

There are reviews24 27,29 on the chemistry of dmit and we present here some of the articles published since Olk’s review29.

The first metal chelates of dmit were reported by Steimecke and coworkers in 1975681. The general method applied to synthesize dmit chelates is the solvolysis of the dibenzoyl compound, (PhCO)2 dmit (160), by methanolic potassium or sodium methanolate followed by an in situ reaction of the generated dithiolate with the corresponding metal salt681 (reaction 167).

The anionic complexes formed can be isolated as crystalline salts using suitable large cations.

Numerous dmit chelates have been synthesized following that route. Although dmit chelates of common metal ions are known, considerable interest has been focused on those of d8 ions (nickel triad). Nickel chelates are listed in Tables 26 and 27. Table 28 summarizes all other salts of bis-chelates of dmit, including the other two elements of nickel triad, palladium and platinum.

There are some studies about neutral mixed-ligand chelates of dmit in which there is interligand CT, while the dithiolene properties are maintained. These chelates are considered to be suitable for studies of both solid-state conductivity and spectral properties

in solution29. Examples are the neutral mixed-ligand dmit chelates, [M(dmit)L], with L D (cyclopentadiene)2 and M D Ti744,745, Zr744, Hf744, V744 and Nb746. There are also

some recent studies about tris-chelates of dmit, with the metals Re742, W747,748 Mo747 749

and Cu750,751.

Other complexes of thiocarbonyl compounds related to dmit, such as 1,2-dithiole- 3-thione-4,5-dithiolate (dmt, 161)741,744,752, 1,3-dithiole-2-thione-4,5-diselenolate (dsit, or 1,3-thiaselenole-2-thione-4,5-dithiolate (dmits, 163)699 have been

1476 M. T. Molina, M. Ya´nez,˜ O. Mo,´ R. Notario and J.-L. M. Abboud

aTTF D tetrathiafulvalene.

bEDT-TTF D ethylenedithiotetrathiafulvalene. c TBT-TTF D tetrabenzylthiotetrathiafulvalene.

dBPDT-TSF D bis(propylenedithio)tetraselenafulvalene. eOMTSF D bis(tetramethylene)tetraselenafulvalene.

1478 M. T. Molina, M. Ya´nez,˜ O. Mo,´ R. Notario and J.-L. M. Abboud

VI. ACKNOWLEDGMENTS

This review was supported by grants PB 93-0289-C02 and PB 93-0142-C03 from the Spanish D.G.I.C.Y.T.

Technical support from Mr. F. Caballero and Drs. G. Chirico and M. Herreros is most appreciated.

This work is dedicated, in memoriam, to Profs. F. Farina˜ and R. W. Taft.

VII. REFERENCES

1.E. Schaumann, in The Chemistry of Double-bonded Functional Groups (Ed. S. Patai), Chap. 17, Wiley, Chichester, 1989.

2.S. Kato and T. Murai, in The Chemistry of Acid Derivatives (Ed. S. Patai), Wiley, Chichester, 1992.

3.V. A. Usov, L. V. Timokhina and M. G. Voronkov, Sulfur Rep., 12, 95 (1992).

4.V. A. Usov, L. V. Timokhina and M. G. Voronkov, Usp. Khim., 59, 649 (1990).

5.V. A. Usov, L. V. Timokhina and M. G. Voronkov, Russian Chem. Rev., 59, 378 (1990).

6.M. A. Ogliaruso and J. F. Wolfe, in The Chemistry of Acid Derivatives (Ed. S. Patai), Wiley, Chichester, 1991.

7.E. Campaigne, Sulfur Rep., 10, 49 (1990).

8.R. Okazaki, Yuki Gosei Kagaku Kyokaishi, 46, 1149 (1988).

9.W. M. McGregor and D. C. Sherrington, Chem. Soc. Rev., 22, 199 (1993).

10. W. Whittingham, in Comprehensive Organic Functional Group Transformations. (Eds.

A.R. Katritzky, O. Meth-Cohn and C. W. Rees), Vol. 3, Pergamon, Elsevier Science, Amsterdam, 1995.

11.R. P. Steer and V. Ramamurthy, Acc. Chem. Res., 21, 380 (1988).

12.A. Maciejwski and R. P. Steer, Chem. Rev., 93, 67 (1993).

13.M. Sakamoto, S. Watanabe, T. Fujita and N. Tatehiko, Yuki Gosei Kagaku Kyokaishi, 52, 658 (1988).

14.V. P. Rao, Sulfur Rep., 12, 359 (1992).

15.D. Crich and L. Quintero, Chem. Rev., 89, 1413 (1989).

16.F. Minisci, NATO ASI Ser., Ser. A, 197, 303 (1990).

17.N. M. M. Nibbering, S. Ingemann and L. J. de Koning, in Chemistry of Sulphur-containing Functional Groups, (Eds. S. Patai and Z. Rappoport), Wiley, Chichester, 1993.

18.J. B. Peel, in The Chemistry of Sulphonic Acids, Esters and their Derivatives (Eds. S. Patai and

Z.Rappoport), Wiley, Chichester, 1991.

19.J. Simonet, in The Chemistry of Functional Groups. Supplement S: The Chemistry of Sulfurcontaining Functional Groups (Eds. S. Patai and Z. Rappoport), Wiley, Chichester, 1993.

20.Y. Vallee,´ Rev. Heteroat. Chem., 8, 1 (1993).

21.J. K. Terlouw and H. Schwarz, Angew, Chem., 26, 805 (1987).

22.F. W. McLafferty, Science, 247, 925 (1990).

23.R. D. McCullough, J. A. Belot, A. L. Rheingold and G. P. A. Yap, J. Am. Chem. Soc., 117, 9913 (1995).

24.P. Cassoux and L. Valade, in Inorganic Materials (Eds. D. W. Bruce and D. O’Hare), Wiley, New York, 1992.

25.P. Cassoux, L. Valade, H. Kobayashi, A. Kobayashi, R. A. Clark and A. E. Underhill, Coord. Chem. Rev., 110, 115 (1991).

26.P. Cassoux and L. V. Interrante, Comments Inorg. Chem., 12, 47 (1991).

27.A. E. Underhill, P. I. Clemenson and R. A. Clark, Pure Appl. Chem., 61, 953 (1989).

28.E. S. Raper, Coord. Chem. Rev., 129, 91 (1994).

29.R.-M. Olk, B. Olk, W. Dietzsch, R. Kirmse and E. Hoyer, Coord. Chem. Rev., 117, 99 (1992).

30.L. Linford and H. G. Raubenheimer, Comments Inorg. Chem., 12, 113 (1991).

31.C. H. Patterson and R. P. Messmer, J. Am. Chem. Soc., 112, 4138 (1990).

32.E. Magnusson, J. Am. Chem. Soc., 112, 7951 (1990).

33.E. Magnusson, J. Am. Chem. Soc., 115, 1051 (1993).

34.S. Ikuta, J. Mol. Struct. (THEOCHEM), 205, 191 (1990).

35.J. Leszczynski, J. Phys. Chem., 97, 3520 (1993).

36.C. Alhambra, F. J. Luque, J. Estelrich and M. Orozco, J. Org. Chem., 60, 969 (1995).

37.I. Alkorta, Theoret. Chim. Acta, 89, 1 (1994).

38.B. G. Johnson, P. M. W. Gill and J. A. Pople, J. Chem. Phys., 98, 5612 (1993).

39.J.-L. M. Abboud, O. Mo,´ J. L. G. de Paz, M. Ya´nez,˜ M. Esseffar, W. Bouab, M. El-Mouhtadi, R. Mokhlisse, E, Ballesteros, M. Herreros, H. Homan, C. Lopez-Mardomingo and R. Notario, J. Am. Chem. Soc., 115, 12468 (1993).

40.J. Tyrrell, J. Mol. Struct. (THEOCHEM), 231, 87 (1991).

41.A. G. Csaszar, Chem. Phys. Lett., 162, 361 (1989).

42.O. Mo,´ M. Ya´nez,˜ M. Esseffar and J.-L. M. Abboud, J. Phys. Org. Chem., 7, 685 (1994).

43.(a) R. F. W. Bader, Atoms in Molecules. A Quantum Theory, Oxford University Press New York, 1990.

(b) R. F. W. Bader, P. J. MacGougall and C. H. Lau, J. Am. Chem. Soc., 106, 1594 (1984).

(c)R. F. W. Bader and C. Chang, J. Phys. Chem., 93, 2946 (1989).

(d)R. F. W. Bader, J. R. Cheeseman, K. E. Laidig, K. B. Wiberg and C. Breneman, J. Am. Chem. Soc., 112, 6530 (1990).

44.J. Hertzinger and M. S. Gordon, J. Phys. Chem., 91, 2353 (1987).

45.A. L. Llamas-Saiz, C. Foces-Foces, O. Mo,´ M. Ya´nez,˜ E. Elguero and J. Elguero, J. Comput. Chem., 16, 263 (1995).

46.D. Christen, H. Oberhammer, W. Zeil, A. Haas and A. Darmadi, J. Mol. Struct., 66, 203 (1980).

47.A. J. Carelless, W. H. Kroto and B. M. Landsberg, Chem. Phys., 1, 371 (1973).

48.M. Nakata, T. Fukuyama and K. Kuchitsu, J. Mol. Struct., 81, 121 (1982).

49.J. H. Carpenter, D. F. Rimmer, J. G. Smith and D. H. Whiffen, J. Chem. Soc., Faraday Trans., 71, 1752 (1975).

50.I. E. Coop and L. E. Sutton, Trans. Faraday Soc., 35, 505 (1939).

51.D. J. Christen, J. Mol. Struct., 66, 211 (1980).

52.J. S. Kwiatkowski and J. Leszczynski, J. Phys. Chem., 97, 1845 (1993).

53.J. S. Craw and G. B. Bacskay, J. Chem. Soc., Faraday Trans., 88, 2315 (1992).

54.L. Gonzalez, O. Mo´ and M. Ya´nez,˜ to appear.

55.R. Janoschek, B. A. Hess Jr. and J. Fabian, Z. Chemie, 30, 176 (1990).

56.L. Gonzalez,´ O. Mo´ and M. Ya´nez,˜ Chem. Phys. Lett., in press.

57.J. D. Goddard, J. Comput. Chem., 8, 389 (1987).

58.J. M. L. Martin, J. P. Francois and R. Gibels, J. Mol. Struct., 168, 363 (1994).

59.S. W. Chiu, W-K. Li, W-B. Tzeng and C-Y. Ng, J. Chem. Phys., 97, 6557 (1992).

60.W. J. Hehre, L. Radom, P. v. R. Scheleyer and J. A. Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986.

61.L. Lapinski, M. J. Nowak, J. Fulara, A. Les and L. Adamowicz, J. Phys. Chem., 96, 6250 (1992).

62.O. G. Parchment, N. A. Burton, I. H. Hillier and M. A. Vincent, J. Chem. Soc., Perkin Trans. 2, 861 (1993).

63.M. J. Nowak, L. Lapinski, H. Rostkowska, A. Les and L. Adamowicz, J. Phys. Chem., 94, 7406 (1990).

64.J. A. Pople, M. Head-Gordon and K. Raghavachari, J. Chem. Phys., 87, 5968 (1987).

D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart and J. A. Pople, Gaussian Inc., Pittsburgh, PA, 1993.

66.L. A. Curtiss, R. H. Nobes, J. A. Pople and L. Radom, J. Chem. Phys., 97, 6766 (1992).

67.R. Schulz, A. Schweig, K. Hartke and J. Koster,¨ J. Am. Chem. Soc., 105, 4519 (1983).

68.M. Rodler and A. Bauder, Chem. Phys Lett., 114, 575 (1985).

69.F. Diehl, H. Schweig, B. A. Hess Jr. and J. Fabian, J. Am. Chem. Soc., 111, 7651 (1989).

70.V. Jonas and G. Frenking, Chem. Phys. Lett., 177, 175 (1991).

71.L. A. Curtiss, J. E. Carpenter, K. Raghavachari and J. A. Pople, J. Chem. Phys., 96, 9030 (1992).

72.M. Esseffar, O. Mo´ and M. Ya´nez,˜ J. Chem. Phys., 101, 2175 (1994).

73.G. Pilcher, in The Chemistry of Acid Derivatives: Supplement B 2, (Ed. S. Patai), Wiley, Chichester, 1992.

74.S. W. Benson, Chem. Rev., 78, 23 (1978).

75.B. Ruscic and J. Berkowitz, J. Chem. Phys., 98, 2568 (1993).

76.J. B. Pedley, R. D. Naylor and S. P. Kirby, Thermochemical Data of Organic Compounds, 2nd edn., Chapman and Hall, London, 1986.

1480 M. T. Molina, M. Ya´nez,˜ O. Mo,´ R. Notario and J.-L. M. Abboud

77.L. A. F. Torres, R. Sabbah and R. Gomez,´ Thermochim. Acta, 58, 311 (1982).

78.P. M. Guyon, W. A. Chupka and J. Berkowitz, J. Chem. Phys., 64, 1419 (1976) and references cited therein.

79.R. K. Lengel and R. N. Zare, J. Am. Chem. Soc., 100, 7495 (1978).

80.N. L. Ma, B. J. Smith, J. A. Pople and L. Radom, J. Am. Chem. Soc., 113, 7903 (1991).

81.P. v. R. Schleyer and D. Kost, J. Am. Chem. Soc., 110, 2105 (1988).

82.M. W. Schmidt, P. N. Truong and M. S. Gordon, J. Am. Chem. Soc., 109, 5217 (1987).

83.K. B. Wiberg and P. Rablen, J. Am. Chem. Soc., 117, 2201 (1995).

84.K. B. Wiberg and D. Nakaji, J. Am. Chem. Soc., 115, 10658 (1993).

85.K. B. Wiberg, C. M. Hadad, P. Rablen and J. Cioslowski, J. Am. Chem. Soc., 114, 8644 (1992).

86.W. Kutzelnigg, Angew. Chem., Int. Ed. Engl., 23, 272 (1984).

87.R. Notario, unpublished results.

88.R. W. Taft and R. D. Topsom, Prog. Phys. Org. Chem., 16, 1 (1987).

89.G. Pfister-Guillouzo, F. Gracian, A. Senio, F. Bourdon, Y. Vallee´ and J.-L. Ripoll, J. Am. Chem. Soc., 115, 324 (1993).

90.X. Creary, Y-X. Wang and Z. Jiang, J. Am. Chem. Soc., 117, 3044 (1995).

91.(a) S. M. Bachrach and M. Liu, J. Phys. Org. Chem., 4, 242 (1991).

(b)P. Burk, J.-L. M. Abboud and I. A. Koppel, J. Phys. Chem., 100, 6992 (1996).

92.V. K. Yadav, A. Yadav and R. A. Poirier, J. Mol. Struct. (THEOCHEM), 186, 101 (1989).

93.P. V. Sudhakar and J. Chandrasekhar, J. Mol. Struc., 194, 135 (1989).

94.L. Goodman and A. G. Ozkabak, J. Mol. Struct. (THEOCHEM), 261, 367 (1992).

95.R. Fausto, J. J. C. Teixeira-Dias and P. R. Carey, J. Mol. Struct. (THEOCHEM), 168, 179 (1988).

96.F. Ramondo and L. Bencivenni, J. Chem. Soc., Perkin Trans 2, 1985 (1994).

97.J. J. C. Teixeira-Dias and R. Fausto, J. Mol. Struct., 144, 199 (1986).

98.R. Fausto, J. J. C. Teixeira-Dias and P. R. Carey, J. Mol. Struct., 159, 137 (1987).

99.M. Bertone, D. L.J. Vuckovic,´ A. Cunje, C. F. Rodriguez, E. Lee-Ruff and A. C. Hopkinson, Can. J. Chem., 73, 1468 (1995).

100.D. J. Clouthier and D. C. Moule, Top. Curr. Chem., 150, 167 (1989).

101.H.-G. Mack, H. Oberhammer and A. Waterfeld, J. Mol. Struct., 249, 297 (1991).

102.E. Auberg, S. Samdal and H. M. Seip, J. Mol. Struct., 57, 95 (1979).

103.A. Almenningen, L. Fernholt, H. M. Seip and L. Henricksen, Acta. Chem. Scand., Ser. A, 28, 1037 (1974).

104.(a) J.-L. M. Abboud, T. Canada,˜ H. Homan, R. Notario, C. Cativiela, M. D. Diaz de Villegas, M. C. Bordeje,´ O. Mo´ and M. Ya´nez,˜ J. Am. Chem. Soc., 114, 4728 (1992).

(b)M. C. Bordeje,´ O. Mo,´ M. Ya´nez,˜ M. Herreros and J.-L. M. Abboud, J. Am. Chem. Soc., 115, 7389 (1993).

105.R. D. Brown, K. G. Dyall, P. S. Elmes, P. D. Godfrey and D. McNaughton, J. Am. Chem. Soc., 110, 789 (1988).

106.C. N. Jarman and H. W. Kroto, J. Chem. Soc., Faraday Trans., 87, 1815 (1991).

107.T. Machiguchi, T. Hasegawa and Y. Kano, Bull. Chem. Soc. Jpn., 66, 3699 (1993).

108.G. P. Raine, H. F. Schaffer III and R. C. Haddon, J. Am. Chem. Soc., 105, 194 (1983).

109.H. Lumbroso and J. Cure,´ J. Mol. Struct., 239, 219 (1990).

110.V. Ferreti, V. Bertolasi, P. Gilli and G. Gilli, J. Phys. Chem., 97, 13568 (1993).

111.(a) M. Feigel and T. Strassner, J. Mol. Struct. (THEOCHEM), 283, 33 (1993).

(b)M.-C. Ou, M.-S. Tsai and S.-Y. Chu J. Mol. Struct. (THEOCHEM), 310, 247 (1994).

112.J. L. Derissen J. Mol. Struct., 7, 81 (1971).

113.D. L. Stiefvater J. Chem. Phys., 62, 233, 244 (1975).

114.K. B. Wiberg, J. Am. Chem. Soc., 108, 5817 (1986).

115.(a) L. A. E. Batista de Carvalho, J. J. C. Teixeira-Dias and R. Fausto, J. Mol. Struct. (THEOCHEM), 208, 109 (1990).

(b)J. J. C. Teixeira-Dias, R. Fausto and L. A. E. Batista de Carvalho, J. Mol. Struct.

(THEOCHEM), 262, 87 (1992).

´

116. M. Alcami, O. Mo´ and M. Ya´nez,˜ Modeling Intrinsic Basicities: The Use of Electrostatic Potentials and the Atoms-in-Molecules Theory, in Molecular Electrostatic Potentials: Concepts and Applications (J. S. Murray and K. Sen, Eds.). Elsevier, Amsterdam 1996. Page 407.

117. M. T. Nguyen, W. D. Weringa and T.-K. Ha, J. Phys. Chem., 93, 7956 (1989).

118. R. Fausto, L. A. E. Batista de Carvalho J. J. C. Teixeira-Dias and M. N. Ramos, J. Chem. Soc., Faraday Trans. 2, 85, 1945 (1989).

119.P. Beak, F. S. Fry Jr., J. Lee and F. Steele, J. Am. Chem. Soc., 98, 171 (1976).

120.P. Beak, J. Covington and J. M. White J. Org. Chem., 45, 1347 (1980).

121.J. Elguero, C. Marzin, A. R. Katrizky and P. Linda, The Tautomerism of Heterocycles, in Adv. Heterocycl. Chem. Suppl. 1 (Eds. A. R. Katrisky and A. J. Boulton), Academic Press, New York, 1976.

122.S. Stoyanov, I, Petrov, L. Antonov, T. Stoyanova, P. Karagiannidis and P. Aslanidis, Can. J. Chem., 68, 1482 (1990).

123.M. J. Nowak, L. Lapinski, J. Fulara, A. Les and L. Adamowicz, J. Phys. Chem., 95, 2404 (1991).

124.M. J. Nowak, H. Rostkowska, L. Lapinski, J. Leszczynski and J. S. Kwiatowski, Spectrochim. Acta, 47A, 339 (1991).

125.J. G. Contreras and J. B. Alderete, Chem. Phys. Lett., 232, 61 (1995).

126.J. G. Contreras and J. Alderete, J. Mol. Struct. (THEOCHEM), 231, 257 (1991).

127.M. W. Wong, K. B. Wiberg and M. J. Frisch, J. Am. Chem. Soc., 114, 1645 (1992).

128.C. Santhosh and P. C. Mishra, Spectrochim. Acta, 49A, 985 (1993).

129.J. G. Contreras and J. B. Alderete, J. Mol. Struct. (THEOCHEM), 283, 283 (1993).

130.J. G. Contreras and J. B. Alderete, J. Mol. Struct. (THEOCHEM), 309, 137 (1994).

131.J. G. Contreras and J. B. Alderete, J. Mol. Struct. (THEOCHEM), 334, 223 (1995).

132.H. Rostkowska, M. J. Nowak, L. Lapinski, M. Brenet, T. Kulikowski, A. Les` and L. Adamowicz, Spectrochim. Acta, 49A, 551 (1993).

133.H. Rostkowska, A. Barski, K. Szczepaniak, M. Szczesniak and W. B. Person, J. Mol. Struct., 176, 137 (1988).

134.H. Rostkowska, K. Szczepaniak, M. J. Nowak, J. Leszczynski, K. Bulat and W. B. Person, J. Am. Chem. Soc., 112, 2147 (1990).

135.A. Les and L. Adamowicz, J. Am. Chem. Soc., 112, 1504 (1990).

136.H. G. M. Edwards, A. F. Johnson and E. E. Lawson, J. Mol. Struct., 351, 51 (1995).

137.S. Millefiori and A. Millefiori, J. Mol. Struct., 151, 373 (1987).

138.F. Diehl, H. Meyer, A. Schweig, B. A. Hess Jr. and J. Fabian, J. Am. Chem. Soc., 111, 7651 (1989).

139.M. Mann and J. Fabian, J. Mol. Struct. (THEOCHEM), 331, 51 (1995).

140.A. Toro-Labbe,´ J. Mol. Struct. (THEOCHEM), 207, 247 (1990).

141.C. Cimiraglia, J. Fabian and B. A. Hess Jr., J. Mol. Struct. (THEOCHEM), 230, 287 (1991).

142.S. Millefiori and A. Millefiori, J. Chem. Soc., Faraday Trans. 2, 85, 1465 (1989).

143.R. Rein, V. Renugopalakrisnan, S. Sir and T. Y. Swissler, Int. J. Quantum Chem., Biol. Symp., 2, 99 (1970).

144.O. Sinanoglu in Molecular Association in Biology (Ed. B. Pullman), Academic Press, New York, 1968.

145.S. Millefiori and S. Di Bella, J. Chem. Soc., Faraday Trans., 87, 1297 (1991).

146.G. Buemi, J. Mol. Struct. (THEOCHEM), 208, 253 (1990).

147.G. Buemi, J. Chem. Soc., Faraday Trans., 85, 1771 (1989).

148.G. Buemi, J. Chem. Soc., Faraday Trans., 86, 2813 (1990).

149.D. R. Johnson and F. X. Powell, Science, 169, 679 (1970).

150.R. Engler and G. Gattow, Z. Anorg. Allg. Chem., 388, 78 (1972).

151.R. H. Judge and G. W. King, Can. J. Phys., 53, 1927 (1975).

152.P. Jensen and P. R. Bunker, J. Mol. Spectrosc., 95, 92 (1982).

153.J. R. Dunlop, J. Karolczak, D. J. Clouthier and S. C. Ross, J. Phys. Chem., 95, 3045 (1991).

154.D. J. Clouthier and D. A. Ramsay, Annu. Rev. Phys. Chem., 34, 31 (1983).

155.P. Jensen and P. R. Bunker, J. Mol. Spectrosc., 94, 114 (1982).

156.P. H. Turner, L. Halonen and I. M. Mills, J. Mol. Spectrosc., 88, 402 (1981).

157.D. J. Clouthier, M. L. Kerr and D. A. Ramsay, Chem. Phys., 56, 73 (1983).

158.D. McNaughton and D. N. Bruget, J. Mol. Spectrosc., 159, 340 (1993).

159.J. Leszczynski, J. S. Kwiatowski and D. Leszczynska, Chem. Phys. Lett., 194, 157 (1992).

160.C. E. Blom, P. J. Slingerland and C. Altona, Mol. Phys., 31, 1359 (1976).

161.C. E. Blom and C. Altona, Mol. Phys., 31, 1377 (1976).

162.C. O. Kappe, M. Wah Wong and C. Wentrup, Tetrahedron Lett., 34, 6623 (1993).

163.D. J. Clouthier and C. Moule, J. Am. Chem. Soc., 109, 6259 (1987).

164.M. Winnewisser and E. Schafer,¨ Z. Naturforsch., Teil A, 35, 483 (1980).

165.J. L. Duncan and C. N. Jarman, Struct. Chem., 1, 195 (1990).

166.H. W. Kroto and D. McNaughton, J. Mol. Spectrosc., 125, 196 (1987).

1482 M. T. Molina, M. Ya´nez,˜ O. Mo,´ R. Notario and J.-L. M. Abboud

167.J. Leszczynski and J. S. Kwiatowski, Chem. Phys. Lett., 201, 79 (1993).

168.C. D. Dyer, J. D. Kilburn, W. F. Maddams and P. A. Walter, Spectrochim. Acta, 47A, 1225 (1991).

169.A. Somogyi, J. Jalsowszky, C. Fulop, J. Stark and J. E. Boggs, Spectrochim. Acta, 45A, 679 (1989).

170.O. Grupce, G. Jovanovski and B. Soptrajanov, J. Mol. Struct., 293, 113 (1993).

171.A. Bigotto, Spectrosc. Lett., 24, 69 (1991).

172.D. N. Sathyanarayana, S. V. Kasmirraja and R. Shummugam, Spectrochim. Acta, 43A, 501 (1987).

173.K. Dwarakanath and D. N. Sathyanarayana, Bull. Chem. Soc. Jpn., 52, 2690 (1979).

174.K. Geetharani and D. N. Sathyanarayana, Ind. J. Chem., 14A, 925 (1976).

175.H. F. Shurvell, R. D. Gordon and R. B. Girling, Spectrochim. Acta, 45A, 305 (1989).

176.D. Sulzle¨ and H. Schwarz, Angew. Chem., Int. Ed. Engl., 27, 1337 (1988).

177.G. Maier, H. P. Reisenauer, J. Schrot and R. Janoschek, Angew. Chem., Int. Ed. Engl., 29, 1464 (1990).

178.C. Wentrup, P. Kambouris, R. A. Evans, D. Owen, G. Macfarlane, J. Chuche, J. C. Pommelet, A. Ben Cheikh, M. Plisnier and R. Flammang, J. Am. Chem. Soc., 113, 3130 (1991).

179.R. B. Bohn, Y. Hannaci and L. Andrews, J. Am. Chem. Soc., 114, 6452 (1992).

180.D. Sulzle,¨ Phosphorus, Sulfur, Silicon Relat. Elem., 74, 295 (1993).

181.G. Maier, J. Schrot, H. P. Reisenauer and R. Janoschek, Chem. Ber., 123, 1753 (1990).

182.G. Maier, U. Flogel,¨ H. P. Reisenauer, B. A. Hess, Jr., and L. J. Schaadt, Chem. Ber., 124, 2609 (1991).

183.A. G. Davies and A. G. Neville, J. Chem. Soc., Perkin Trans. 2, 171 (1992).

184.M. A. Cremonini, L. Lunazzi and G. Placucci, J. Org. Chem., 58, 3805 (1993).

185.D. Casarini, L. Lunazzi, G. Placucci, T. Ishida, A. Ishii and R. Okazaki, J. Org. Chem., 53, 1582 (1988).

186.A. Alberti, M. Benaglia, M. C. Depew, W. G. McGimpsey, G. Pedulli and J. K. S. Wan, Tetrahedron, 44, 3693 (1988).

187.G. C. Leo, A. D. Gauthier, G. W. Caldwell and M. J. Kukla, Magn. Reson. Chem., 30, 185 (1992).

188.B. Olk, R.-M. Olk and E. Hoyer, Z. Chem., 30, 105 (1990).

189.F. Duus, Magn. Reson. Chem., 27, 767 (1989).

190.J. Rochester and J. Sandstrom,¨ Tetrahedron, 45, 5081 (1989).

191.G. Barbarella, A. Bongini and S. Rossini, J. Org. Chem., 53, 5140 (1988).

192.G. Barbarella and A. Bongini, Tetrahedron, 45, 5137 (1989).

193.G. A. Olah, T. Nakajima and G. K. Suria Prakash, Angew. Chem., Int. Ed. Engl., 19, 811 (1980).

194.P. V. De Marco and E. Doddrell, J. Chem. Soc., Chem. Commun., 1418 (1969).

195.J. A. Pople, J. Chem. Phys., 37, 53 (1962).

196.A. R. Katritzky, S. Sobiak and C. M. Marson, Org. Magn. Reson., 26, 665 (1988).

197.H.-R. Sliwka and S. Liaanen-Jensen, Acta. Chem. Scand., 48, 679 (1994).

198.R. S. Becker, S. Chakravorty, C. A. Gartner and M. de G. Miguel, J. Chem. Soc., Faraday Trans., 89, 1007 (1993).

199.M. R. J. Hachey and F. Grein, J. Mol. Spectrosc., 172, 384 (1995).

200.M. R. J. Hachey and F. Grein, Chem. Phys., 197, 61 (1995).

201.R. Janoschek, J. Mol. Struct. (THEOCHEM), 232, 147 (1991).

202.G. Maier, H. P. Reisenauer, U. Schafer¨ and H. Balli, Angew. Chem., Int. Ed. Engl., 27, 566 (1988).

203.H. K. Sinha, O. K. Abou-Zied and R. P. Steer, Chem. Phys. Lett., 201, 433 (1993).

204.F. Bourdon, J.-L. Ripoll, Y. Vallee,´ S. Lacombe and G. Pfister-Gullouzo, J. Org. Chem., 55, 2596 (1990).

205.I. B’Shary, C. Guimon, M. Grimaud and G. Pfister-Guillouzo, Can. J. Chem., 66, 2830 (1988).

206.F. Bourdon, J.-L. Ripoll. Y. Vallee,´ S. Lacombe and G. Pfister-Guillouzo, New. J. Chem., 15, 533 (1991).

207.D. H. R. Barton, Tetrahedron, 48, 2529 (1992).

208. F. Minisci, in Sulfur-Centered Reactive Intermediates in Chemistry and Biology (Eds.

C. Chatgilialoglu and K.-D. Asmus), Plenum Press, New York, 1990, p. 303.

209.R. Kh. Freidlina, I. I. Kandror, B. V. Kopylova, R. G. Petrova and T. D. Churkina in Chem. Organosulfur Compd. (Ed. L. I. Belenkii), Horwood, Chichester, 1990, p. 26.

210.D. Crich and L. Quintero, Chem. Rev., 89, 1413 (1989).

211.D. H. R. Barton and N. Ozbalik, Phosphorus, Sulfur, 43, 349 (1989).

212.D. H. R. Barton and N. Ozbalik, J. Chin. Chem. Soc., 35, 247 (1988).

213.D. H. R. Barton and N. Ozbalik, in NATO ASI, Ser. C., Paramagnetic Organometallic Species in Activation/Selectivity, Catalysis, 1 12 M. Chanon, M. Julliard, J.-C. Poite (Eds), Kluwer Academic Publishers, Dordrecht, 1989, p. 257.

214.R. Pauwels, K. Andries, J. Desmyter, D. Schols, M. J. Kukla, H. J. Breslin, A. Raeymaeckers, J. Van Gelder, R. Woestenborghs, J. Heykants, K. Schellekens, M. A. C. Janssen, E. De Clercq and P. A. J. Janssen, Nature, 343, 470 (1990).

215.Heterocyclic thiones: 1,3-dithiole-2-thione-4,5-dithiolate (DMIT). N. Svenstrup and J. Becher, Synthesis, 215 (1995).

216.1,2-dithiole-3-thiones. N. Lozac’h, Sulfur Rep., 9, 153 (1989).

217. 3-cyanopyridin-2(1H)-thiones. V. P. Litvinov, L. A. Rodinovskaya, Yu. A. Sharanin and

A. M. Shestopalov, Sulfur Rep., 13, 1 (1992).

218.1,2,4-triazolidine-3-thiones. V. V. Ovcharenko, V. V. Lashin and P. B. Terentov, Khim, Geterosikl. Soedin., 991 (1993); Chem. Abstr., 120, 106800 (1994).

219.Imidazole-2-thiones. B. V. Trzhtsinskaya and N. D. Abramova, Sulfur Rep., 10, 389 (1991).

220.Dihydro-1,4-benzodiazepin-2(2H)-thiones. A. Walser and R. I. Fryer, Chem. Heterocycl. Compd., 50, 631 (1991).

221.Chiral thiazolidine-2-thiones and oxazolidine-2-thiones. E. Fujita and Y. Nagao, Adv. Heterocycl. Chem., 45, 1 (1989).

222.2-thiopyrones and 2-thiopyridones. K. Afarinkia, V. Vinader, T. D. Nelson and G. H. Posner, Tetrahedron, 48, 9152 (1992).

223.W. M. McGregor and D. C. Sherrington, Chem. Soc. Rev., 199 (1993).

224.G. W. Kirby, Phosphorus, Sulfur, Silicon Relat. Elem., 74, 17 (1993).

225.V. A. Usov, L. V. Timokhina and M. G. Voronkov, Usp. Khim., 59, 649 (1990).

226.P. Metzner, Synthesis, 1185 (1992).

227.E. Block, A. Schwan and D. A. Dixon, J. Am. Chem. Soc., 114, 3492 (1992).

228.T. J. Barton and G. C. Paul, J. Am. Chem. Soc., 109, 5292 (1987).

229.H. Suzuki, N. Tokitoh, S. Nagase and R. Okazaki, J. Am. Chem. Soc., 116, 11578 (1994).

230.E. Schaumann, Tetrahedron, 44, 1827 (1988).

231.R. Appel, P. Folling,¨ L. Krieger, M. Siray and F. Knoch, Angew. Chem., Int. Ed. Engl., 23, 970 (1984).

232.M. S. Raasch, J. Org. Chem., 44, 632 (1979).

233. W. G. Whittingham, in Comprehensive Organic Functional Groups Transformations (Ed.

G. Pattenden), Vol. 3, Pergamon, Elsevier, Oxford, 1995, p. 329.

234.D. C. Harrowven and S. T. Dennison, in Comprehensive Organic Functional Groups Transformations (Ed. G. Pattenden) Vol. 3, p. 525.

235.Zh. A. Krasnaya, Izv. Akad. Nauk SSSR, Ser, Khim., 494 (1986); Chem. Abstr., 106, 4496 (1987).

236.P. Jutzi, K.-H. Schwartzen, A. Mix, H.-G. Stammler and B. Neumann, Chem. Ber., 126, 415 (1993).

237.K. Okuma, Y. Komiya and H. Ohta, Chem. Lett., 1145 (1988); Bull. Chem. Soc. Jpn., 64, 2402 (1991).

238.R. Sato and S. Satoh, Synthesis, 785 (1991).

239.W. M. Abdou, Y. O. Elkhoshnieh and M. M. Sidky, Tetrahedron, 50, 3595 (1994).

240.D. Brillon, Sulfur Rep., 12, 297 (1992).

241.B. S. Pedersen, S. Scheibye, N. H. Nilsson and S.-O. Lawesson, Bull. Soc. Chim. Belg., 87, 223 (1978).

242.Review: M. P. Cava and M. I. Levinson, Tetrahedron, 41, 5061 (1985).

243.Review: M. Pulst, D. Greif and E. Kleinpeter, Z. Chem., 28, 345 (1988).

244.Review: V. I. Filyakova, I. G. Busygin, L. N. Bazhenova, V. E. Kirichenko and K. I. Pashkevich, Enaminy Org. Synt., 70 (1990); Chem. Abstr., 114, 228306 (1991).

245.V. Sachweh and H. Langhals, Chem. Ber., 123, 1981 (1990).

246.E. Campaigne and W. B. Reid, Jr., J. Am. Chem. Soc., 68, 769 (1946).

247.P. S. Portoghese, A. Garzon-Aburbeh, H. Nagase, C.-E. Lin and A. E. Takemori, J. Med. Chem., 34, 1292 (1991).

248.J. Becher, P. L. Jørgensen, H. Frydendahl and B. Falt¨-Hansen, Synthesis, 609 (1991).

249.B. F. Bonini, Phosphorus, Sulfur, Silicon Relat. Elem., 74, 31 (1993).

1484 M. T. Molina, M. Ya´nez,˜ O. Mo,´ R. Notario and J.-L. M. Abboud

250.B. F. Bonini, G. Mazzanti, P. Zani and G. Maccagnani, J. Chem. Soc., Perkin Trans. 1, 2083 (1989).

251.B. F. Bonini, M. Comes-Franchini, G. Mazzanti, A. Ricci, L. Rosa-Fauzza and P. Zani, Tetrahedron Lett., 35, 9227 (1994).

252.J. W. Scheeren, P. H. J. Ooms and R. J. F. Nivard, Synthesis, 149 (1973).

253.K. J. Falk and R. P. Steer, Can. J. Chem., 66, 575 (1988).

254.N. H. Werstiuk, S. Yeroushalmi and H. Guan-Lin, Can. J. Chem., 70, 974 (1992).

255.A. J. Moore and M. R. Bryce, J. Chem. Soc., Perkin Trans. 1, 157 (1991).

256.M. R. Bryce, M. A. Coffin, M. B. Hursthouse and M. Mazid, Angew. Chem., Int. Ed. Engl., 30, 871 (1991).

257. K. Katano, H. Ogino, K. Iwamatsu, S. Nakabayashi, T. Yoshida, I. Komiya, T. Tsuruoka,

S. Inouye and S. Kondo, J. Antibiotics, 43, 1150 (1990).

258.A. Z.-Q. Khan and J. Sandstr¨om,¨ J. Chem. Soc., Perkin Trans. 1, 2085 (1988).

259.T. Asao, Pure Appl. Chem., 62, 507 (1990).

260.T. Machiguchi, Y. Kano and T. Hasegawa, Chem. Lett., 563 (1990).

261.T. Machiguchi, T. Hasegawa and Y. Kano, Bull. Chem. Soc. Jpn., 66, 3699 (1993).

262.S. Motoki, T. Sakai, Y. Matsuo, S. Kametani and T. Saito, Bull. Chem. Soc. Jpn., 65, 923 (1992).

263.T. Saito, M. Nagashima, T. Karakasa and S. Motoki, J. Chem. Soc., Chem. Commun., 1665 (1990).

264.G. W. Kirby and W. M. McGregor, J. Chem. Soc., Perkin Trans. 1, 3175 (1990).

265.A. Haas and H.-W. Praas, J. Fluorine Chem., 60, 153 (1993).

266.T. B. Rauchfuss and G. A. Zank, Tetrahedron Lett., 27, 3445 (1986).

267.G. Lajoie, F. Lepine,´ L. Maziak and B. Belleau, Tetrahedron Lett., 24, 3815 (1983).

268.M. Yokoyama, Y. Hasegawa, H. Hatanaka, Y. Kawazoe and T. Imamoto, Synthesis, 827 (1984).

269.C. Lemaire, A. Plenevaux, R. Cantineau, L. Christiaens, M. Guillaume and D. Comar, Appl. Radiat. Isot., 44, 737 (1993).

270.A. N. Dixit, K. V. Reddy, A. R. A. S. Deshmukh, S. Rajappa, B. Ganguly and J. Chandrasekhar, Tetrahedron, 51, 1437 (1995).

271.H. Nakazumi, Asahi Garasu Zaidan Josei Kenkyu Seika Hokoku, 153 (1993); Chem. Abstr., 121, 69157 (1994).

272.K.-F. Wai and M. P. Sammes, J. Chem. Soc., Perkin Trans. 1, 183 (1991).

273.A. Reliquet, R. Besbes, F. Reliquet and J. C. Meslin, Synthesis, 543 (1991).

274.M. Alvarez, M. Salas, L. Rigat, A. de Veciana and J. A. Joule, J. Chem. Soc., Perkin Trans. 1, 351 (1992).

275.A. Levai´ and Z. Szabo,´ Bull. Soc. Chim. Fr., 128, 967 (1991).

276.A. Levai,´ J. Chem. Res. (S), 163 (1992).

277.M. Murase, S. Yoshida, T. Hosaka and S. Tobinaga, Chem. Pharm. Bull., 39, 489 (1991).

278.M. Murase, T. Hosaka, T. Koike and S. Tobinaga, Chem. Pharm. Bull., 37, 1999 (1989).

279.M. Murase, T. Hosaka and S. Tobinaga, Heterocycles, 30, 905 (1990).

280.M. R. Detty and B. J. Murray, J. Org. Chem., 47, 1146 (1982); M. R. Detty, Organometallics, 7, 2188 (1988).

281.R. Kuhn¨ and H.-H. Otto, Arch. Pharm., 322, 375 (1989).

282.T. Strehlow, J. Voss, R. Spohnholz and G. Adiwidjaja, Chem. Ber., 124, 1397 (1991).

283.A. Muzaffar, A. Brossi, C. M. Lin and E. Hamel, J. Med. Chem., 33, 567 (1990).

284.A. Muzaffar and A. Brossi, Synth. Commun., 20, 713 (1990).

285.H.-R. Sliwka and S. Liaaen-Jensen, Acta Chem. Scand., 48, 679 (1994).

286.D. Weiss, U. Gaudig and R. Beckert, Synthesis, 751 (1992).

287.J. Nkiliza, J. Vercauteren and J.-M. Leger,´ Tetrahedron Lett., 32, 1787 (1991).

288.Y. Vallee,´ S. Masson and J.-L. Ripoll, Tetrahedron, 46, 3921 (1990).

289.J. Hasserodt, H. Pritzkow and W. Sundermeyer, Chem. Ber., 126, 1701 (1993).

290.A. Z.-Q. Khan and J. Sandstrom,¨ J. Org. Chem, 56, 1902 (1991).

291.A. Z.-Q. Khan, J. Sandstrom,¨ K.-E. Bergquist, C.-Y. Cheng and S.-L. Wang., J. Org. Chem., 56, 4919 (1991).

292.P. Wipf, C. Jenny and H. Heimgartner, Helv. Chim. Acta, 70, 1001 (1987).

293. K. C. Nicolaou, D. G. McGarry, P. K. Somers, B. H. Kim, W. W. Ogilvie, G. Yiannikouros,

C. V. C. Prasad, C. A. Veale and R. R. Hark, J. Am. Chem. Soc., 112, 6263 (1990).

294.H. Davy, J. Chem. Soc., Chem. Commun., 457 (1982).

295.H. Davy and P. Metzner, J. Chem. Res. (S), 272 (1985); J. Chem. Res. (M), 2701 (1985).