Abstract
Abstract CNDO/2 molecular orbital calculations have been performed on the systems [Ru(NX)CI5]2- and [Ru(NX)Cl4(H2O)]− (X = S or O) in order to investigate the nature and energetics of the interaction between ruthenium and isoelectronic NS and NO ligands. The computed trends for Ru-N, NS and NO bond strengths in the complexes, as measured by Wiberg indices, charge distributions and orbital populations, suggest that the strength of the Ru-NS bond is greater than that of the Ru-NO bond and the NS ligand is a better electron remover from the central ruthenium atom than the NO ligand. The strength of an Ru-L (L = Cl or H2O) bond trans to a NS ligand is weaker than a Ru-L bond trans to a NO ligand. The ratio of σ-donor to π-acceptor abilities of NS is greater than that of NO. For [Ru(NX)Cl5]2, the strength of the trans-Ru-Cl bond is greater than that of the cis-Ru-Cl bond for nitrosyl complexes but the reverse is true for thionitrosyl complexes. The calculations confirm the experimental observations that the ligand positioned trans to an NS ligand is more labile and, hence, more susceptible to replacement than the ligand positioned trans to a NO ligand.
Published Version
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