References
257
tives, the two S-S bond-lengths are usually unequal, due presumably to the nature
of the substituent
23
.)
For thiothiophthene, we can use the numerous standard Lewis structures such
as (51), (52) and (53) + mirror images to construct the (more-stable) “increasedvalence” structures (54) and (55) by means of the delocalizations indicated.
Resonance between either set of structures accounts for the lengthening of the S-S
bonds, but additional considerations are required to rationalize the observed
variations in the C-S and C-C bond lengths.
References
1. H.A. Levy and P.A. Agron, J. Amer. Chem. Soc., 85, 241 (1963).
2. E.H. Wiebenga, E.E. Having and K.H. Boswijk, Advances in Inorganic and
Radiochemistry (Academic Press, N.Y.), 3, 133 (1961) and references therein.
3. J.I. Musher, (a) Angewandte Chem. (Int. Ed.), 8, 54 (1969); (b) J. Amer. Chem. Soc.,
94, 1370 (1972); (c) Tetrahedron, 30, 1747 (1974) and references therein.
4. G.C. Pimentel, J. Chem. Phys., 19, 446 (1951).
5. R.J. Hach and R.E. Rundle, J. Amer. Chem. Soc., 73, 4321 (1951).
6. T.A. Halgren, L.D. Brown, D.A. Kleier and W.N. Lipscomb, J. Amer. Chem. Soc., 99,
6793 (1977).
7. G.B. Carpenter, J. Chem. Educ., 40, 385 (1963).
8. R.F. Hudson, Angewandte Chem. (Int. Ed.), 6, 749 (1967).
9. R. Gleiter and R. Hoffmann, Tetrahedron, 24, 5899 (1968).
10. J. Bilham and J.W. Linnett, Nature, 201, 1323 (1964) and unpublished results.
11. N. Bartlett, F. Einstein, D.F. Stewart and J. Trotter, J. Chem. Soc. A, 1190 (1967).
12. D.F. Smith, J. Chem. Phys., 21, 609 (1953).
13. W.M. Tolles and W.D. Gwinn, J. Chem. Phys., 36, 1119 (1962); K. Kimura and S.H.
Bauer, J. Chem. Phys., 39 3172 (1963).
14. K.W. Hansen and L.S. Bartell, Inorg. Chem., 4, 1775 (1965).
15. F.O. Sladky, P.A. Bulliner, N. Bartlett, B.G. de Boer and A. Zalkin, Chem. Comm.,
1048 (1968).
16. J.D. Forrester, M.E. Senko, A. Zalkin and D.H. Templeton, Act.a. Cryst., 16, 58 (1963).
17. R.D. Harcourt, J. Inorg. Nuclear Chem., 39, 237 (1977).
18. G. Bowmaker, Aust. J. Chem. 31, 2713 (1978) and references therein.
19. L.S. Bartell and S.K. Doun, J. Mol. Struct. 43, 245 (1978).
20. R.G.A.R. Maclagan, J. Chem. Educ. 57, 428 (1980).
21. L.S. Bartell and C.J. Marsden, J. Mol. Struct. 75, 271 (1981),
22. L.K. Hansen and A. Hordvik, Acta Chem. Scand., 24, 2246 (1970).
23. A. Hordvik, Acta Chem. Scand., 25, 1583, 1822 (1971).
24. R.D. Harcourt, J. Mol. Struct. THEOCHEM, 684, 167 (2004).
257
tives, the two S-S bond-lengths are usually unequal, due presumably to the nature
of the substituent
23
.)
For thiothiophthene, we can use the numerous standard Lewis structures such
as (51), (52) and (53) + mirror images to construct the (more-stable) “increasedvalence” structures (54) and (55) by means of the delocalizations indicated.
Resonance between either set of structures accounts for the lengthening of the S-S
bonds, but additional considerations are required to rationalize the observed
variations in the C-S and C-C bond lengths.
References
1. H.A. Levy and P.A. Agron, J. Amer. Chem. Soc., 85, 241 (1963).
2. E.H. Wiebenga, E.E. Having and K.H. Boswijk, Advances in Inorganic and
Radiochemistry (Academic Press, N.Y.), 3, 133 (1961) and references therein.
3. J.I. Musher, (a) Angewandte Chem. (Int. Ed.), 8, 54 (1969); (b) J. Amer. Chem. Soc.,
94, 1370 (1972); (c) Tetrahedron, 30, 1747 (1974) and references therein.
4. G.C. Pimentel, J. Chem. Phys., 19, 446 (1951).
5. R.J. Hach and R.E. Rundle, J. Amer. Chem. Soc., 73, 4321 (1951).
6. T.A. Halgren, L.D. Brown, D.A. Kleier and W.N. Lipscomb, J. Amer. Chem. Soc., 99,
6793 (1977).
7. G.B. Carpenter, J. Chem. Educ., 40, 385 (1963).
8. R.F. Hudson, Angewandte Chem. (Int. Ed.), 6, 749 (1967).
9. R. Gleiter and R. Hoffmann, Tetrahedron, 24, 5899 (1968).
10. J. Bilham and J.W. Linnett, Nature, 201, 1323 (1964) and unpublished results.
11. N. Bartlett, F. Einstein, D.F. Stewart and J. Trotter, J. Chem. Soc. A, 1190 (1967).
12. D.F. Smith, J. Chem. Phys., 21, 609 (1953).
13. W.M. Tolles and W.D. Gwinn, J. Chem. Phys., 36, 1119 (1962); K. Kimura and S.H.
Bauer, J. Chem. Phys., 39 3172 (1963).
14. K.W. Hansen and L.S. Bartell, Inorg. Chem., 4, 1775 (1965).
15. F.O. Sladky, P.A. Bulliner, N. Bartlett, B.G. de Boer and A. Zalkin, Chem. Comm.,
1048 (1968).
16. J.D. Forrester, M.E. Senko, A. Zalkin and D.H. Templeton, Act.a. Cryst., 16, 58 (1963).
17. R.D. Harcourt, J. Inorg. Nuclear Chem., 39, 237 (1977).
18. G. Bowmaker, Aust. J. Chem. 31, 2713 (1978) and references therein.
19. L.S. Bartell and S.K. Doun, J. Mol. Struct. 43, 245 (1978).
20. R.G.A.R. Maclagan, J. Chem. Educ. 57, 428 (1980).
21. L.S. Bartell and C.J. Marsden, J. Mol. Struct. 75, 271 (1981),
22. L.K. Hansen and A. Hordvik, Acta Chem. Scand., 24, 2246 (1970).
23. A. Hordvik, Acta Chem. Scand., 25, 1583, 1822 (1971).
24. R.D. Harcourt, J. Mol. Struct. THEOCHEM, 684, 167 (2004).