230
Chapter 17 Some Tetrahedral Molecules
16. Y. Kawashima and A.P. Cox, J. Mol. Spectr., 65, 319 (1977).
17. See for example J.R. Rea and F. Kostiner, Acta Cryst B28, 3461 (1972).
18. L. Pauling, The Nature of the Chemical Bond (Cornell 1960), p. 321.
19. R. Steudel, Angewandte Chem. (Int. Ed.), 14, 655 (1975) and references therein.
20. C. Th. Kiers, A. Piepenbroek and A. Vos., Acta Cryst. B34, 888 (1978).
21. S. Baggio, Acta Cryst. B27, 517 (1971).
22. J.D. Dunitz, Acta Cryst. 9, 579 (1956).
Addendum Chapter 17
In Refs. 23 and 24, further consideration is given to valence-bond structures that
involve expansion of the valence shell for second-row and higher-row elements -
for example the use of sulphur 3d orbitals as valence orbitals in SF 6 . See also Ref.
25 for another type of SF 6 increased-valence structures that does not involve
expansion of the sulphur valence shell. In Ref. 26, increased-valence structures are
presented for OSSSO (see also Ref. 27) and O 2 SSSO 2 with two tetrahedral sulphur
atoms.
For phosphorus, sulphur and chlorine (and other main-group element) atoms,
“it has been shown by many researchers that d orbitals do not act primarily as
valence-shell orbitals but instead as polarization functions or as acceptor orbitals
for back-donation from the ligands, thus disproving the expanded octet model”
28
,
i.e. for these atoms, one should speak of “d functions, not d orbitals”
29
.
23. R.D. Harcourt, J. Mol. Struct. (Theochem) 186, 131 (1989).
24. R.D. Harcourt and T.M. Klapötke, J. Fluor. Chem. 123, 5 (2003).
25. R.D. Harcourt, J. Phys. Chem. A, 115, 6610, 8180 (2011).
26. D.B. Chesnut, L.J. Bartolotti and R.D. Harcourt, J. Phys. Chem. A, 113, 8677 (2009).
27. R.D. Harcourt, Inorg. Chem. 46, 5773 (2007).
28. B. Braida, T. Ribeyre and P.C. Hiberty, Chem. Eur. J. 20, 9643 (2014), and Refs. 4 and
5 therein, and Ref. 29 below.
29. E. Magnusson, J. Am. Chem. Soc. 112, 7940 (1990).
Chapter 17 Some Tetrahedral Molecules
16. Y. Kawashima and A.P. Cox, J. Mol. Spectr., 65, 319 (1977).
17. See for example J.R. Rea and F. Kostiner, Acta Cryst B28, 3461 (1972).
18. L. Pauling, The Nature of the Chemical Bond (Cornell 1960), p. 321.
19. R. Steudel, Angewandte Chem. (Int. Ed.), 14, 655 (1975) and references therein.
20. C. Th. Kiers, A. Piepenbroek and A. Vos., Acta Cryst. B34, 888 (1978).
21. S. Baggio, Acta Cryst. B27, 517 (1971).
22. J.D. Dunitz, Acta Cryst. 9, 579 (1956).
Addendum Chapter 17
In Refs. 23 and 24, further consideration is given to valence-bond structures that
involve expansion of the valence shell for second-row and higher-row elements -
for example the use of sulphur 3d orbitals as valence orbitals in SF 6 . See also Ref.
25 for another type of SF 6 increased-valence structures that does not involve
expansion of the sulphur valence shell. In Ref. 26, increased-valence structures are
presented for OSSSO (see also Ref. 27) and O 2 SSSO 2 with two tetrahedral sulphur
atoms.
For phosphorus, sulphur and chlorine (and other main-group element) atoms,
“it has been shown by many researchers that d orbitals do not act primarily as
valence-shell orbitals but instead as polarization functions or as acceptor orbitals
for back-donation from the ligands, thus disproving the expanded octet model”
28
,
i.e. for these atoms, one should speak of “d functions, not d orbitals”
29
.
23. R.D. Harcourt, J. Mol. Struct. (Theochem) 186, 131 (1989).
24. R.D. Harcourt and T.M. Klapötke, J. Fluor. Chem. 123, 5 (2003).
25. R.D. Harcourt, J. Phys. Chem. A, 115, 6610, 8180 (2011).
26. D.B. Chesnut, L.J. Bartolotti and R.D. Harcourt, J. Phys. Chem. A, 113, 8677 (2009).
27. R.D. Harcourt, Inorg. Chem. 46, 5773 (2007).
28. B. Braida, T. Ribeyre and P.C. Hiberty, Chem. Eur. J. 20, 9643 (2014), and Refs. 4 and
5 therein, and Ref. 29 below.
29. E. Magnusson, J. Am. Chem. Soc. 112, 7940 (1990).