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Issue 13, 1997
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Chemical bonding in oxofluorides of hypercoordinatesulfur

Abstract

Modern valence bond theory, in its spin-coupled form, is used to investigate the bonding in sulfuryl fluoride, SO 2 F 2 , and in the thionyl fluorides, SOF 2 and SOF 4 . Analogous calculations are also carried out for SO 2 , SO 3 and SF 4 , to enable various comparisons to be made. We find that the sulfur atoms in these systems utilize all six valence electrons in two-centre two-electron polar covalent bonds and in angularly split lone-pair-like orbitals. Although based on just a single orbital configuration, the spin-coupled wavefunction provides a significant energy improvement over the corresponding restricted Hartree–Fock calculation. The spin-coupled description of the S[double bond, length as m-dash]O and S–F bonding, and of the non-bonding electrons on sulfur, turns out to be highly transferable. We find that the S–O π bonds are significantly more polar than the S–O σ bonds. We find no evidence to support notions of p π –d π back-donation from oxygen to sulfur. We examine also the ‘equivalent’ or ‘bent-bond’ model of the SO units in the thionyl fluorides.

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Article type: Paper
DOI: 10.1039/A700708F
Citation: J. Chem. Soc., Faraday Trans., 1997,93, 2247-2254
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    Chemical bonding in oxofluorides of hypercoordinate sulfur

    T. P. Cunningham, D. L. Cooper, J. Gerratt, P. B. Karadakov and M. Raimondi, J. Chem. Soc., Faraday Trans., 1997, 93, 2247
    DOI: 10.1039/A700708F

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