References
229
For each
3
SO
linkage of structures (48), (50) and (51), we have indicated
delocalizations of two O
– electrons into sulphur 3d orbitals. A small amount of
delocalization of O
– electrons into bonding S-O orbitals will also occur (cf. structure (37) for
2
4
SO
).
The valence-bond structures (48)-(51) suggest that the S-S lengths should increase in the order
2
2
2
2
2 3
2 6
2 5
2 4
S O
S O
S O
S O
, and the measured lengths
19-22
of 1.97 Å, 2.08-2.16 Å, 2.17 Å and 2.39 Å show this to be the case. For
2
2 3
S O
,
the two d π – p π bonds should be delocalized fairly evenly over the S-S and three SO bonds, to give bond-numbers of 1.5 for each bond.
References
1. T.A. Halgren, L.D. Brown, D.A. Kleier and W.N. Lipscomb, J. Amer. Chem. Soc., 99,
6793 (1977).
2. D.P. Craig, A. Maccoll, R.S. Nyholm and L.E. Orgel, J. Chem. SOc. , 354 (1954).
3. D.W.J. Cruickshank, J. Chem. Soc., 5486 (1961).332
4. (a) C.A. Coulson, Nature, 221, 1106 (1969); (b) K.A.R. Mitchell, Chem. Revs., 69,
157 (1969).
5. H. Kwart and K.G. King, “d-Orbitals in the Chemistry of Silicon, Phosphorus and
Sulfur” (Springer-Verlag 1977).
6. R.G.A.R. Maclagan, J. Chem. Educ., 57, 428 (1980) and references therein.
7. Feder, H. Driezler, H.D. Rudolph and N. Typke, Z. Naturforsch., 24a, 266 (1969).
8. J. Kojima and T. Nishikawa, J. Phys. Soc. Jap., 12, 680 (1957).
9. V. Plato, W.D. Hartford and K. Hedberg, J. Chem. Phys., 53, 3438 (1970).
10. A. Caron, G.J. Palenik, E. Goldish and J. Donohue, Acta. Cryst., 17, 102 (1964).
11. O. Glemser, Angewandte Chem. (Int. Ed.), 2, 530 (1973).
12. (a) W.H. Kirchhoff and E.B. Wilson, Jnr., J. Amer. Chem. Soc., 84, 334 (1962); (b)
C.E. Small and J.G. Smith, Mol. Phys. 37, 615 (1979).
13. A.G. Nord, Acta Chem. Scand., 27, 814 (1973).
14. M. Jansen, Angewandte Chem. (Int. Ed.), 18, 698 (1979).
15. R.H. Kagann, I. Ozier and M.C.L. Gerry, Chem. Phys. Letts., 47, 572 (1977).
229
For each
3
SO
linkage of structures (48), (50) and (51), we have indicated
delocalizations of two O
– electrons into sulphur 3d orbitals. A small amount of
delocalization of O
– electrons into bonding S-O orbitals will also occur (cf. structure (37) for
2
4
SO
).
The valence-bond structures (48)-(51) suggest that the S-S lengths should increase in the order
2
2
2
2
2 3
2 6
2 5
2 4
S O
S O
S O
S O
, and the measured lengths
19-22
of 1.97 Å, 2.08-2.16 Å, 2.17 Å and 2.39 Å show this to be the case. For
2
2 3
S O
,
the two d π – p π bonds should be delocalized fairly evenly over the S-S and three SO bonds, to give bond-numbers of 1.5 for each bond.
References
1. T.A. Halgren, L.D. Brown, D.A. Kleier and W.N. Lipscomb, J. Amer. Chem. Soc., 99,
6793 (1977).
2. D.P. Craig, A. Maccoll, R.S. Nyholm and L.E. Orgel, J. Chem. SOc. , 354 (1954).
3. D.W.J. Cruickshank, J. Chem. Soc., 5486 (1961).332
4. (a) C.A. Coulson, Nature, 221, 1106 (1969); (b) K.A.R. Mitchell, Chem. Revs., 69,
157 (1969).
5. H. Kwart and K.G. King, “d-Orbitals in the Chemistry of Silicon, Phosphorus and
Sulfur” (Springer-Verlag 1977).
6. R.G.A.R. Maclagan, J. Chem. Educ., 57, 428 (1980) and references therein.
7. Feder, H. Driezler, H.D. Rudolph and N. Typke, Z. Naturforsch., 24a, 266 (1969).
8. J. Kojima and T. Nishikawa, J. Phys. Soc. Jap., 12, 680 (1957).
9. V. Plato, W.D. Hartford and K. Hedberg, J. Chem. Phys., 53, 3438 (1970).
10. A. Caron, G.J. Palenik, E. Goldish and J. Donohue, Acta. Cryst., 17, 102 (1964).
11. O. Glemser, Angewandte Chem. (Int. Ed.), 2, 530 (1973).
12. (a) W.H. Kirchhoff and E.B. Wilson, Jnr., J. Amer. Chem. Soc., 84, 334 (1962); (b)
C.E. Small and J.G. Smith, Mol. Phys. 37, 615 (1979).
13. A.G. Nord, Acta Chem. Scand., 27, 814 (1973).
14. M. Jansen, Angewandte Chem. (Int. Ed.), 18, 698 (1979).
15. R.H. Kagann, I. Ozier and M.C.L. Gerry, Chem. Phys. Letts., 47, 572 (1977).