Structural data obtained from published single-crystal X-ray studies of molecular transition metal complexes of terminal thiophenolate ligands are used to rationalize a model for M-S π bonding. The principal π-donor orbital of thiolates is the S 3p orbital which is oriented perpendicular to the M-S-C plane. Consequently, M-S-C bond angles are not indicative of the degree of M-S dπ-pπ bonding.
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Michael T. Ashby (1990) studied this question.
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