ORGANOMETALLIC THIOL AND THIOLATO COMPLEXES OF RUTHENIUM(IV)

Reaction of the ruthenium(IV) chloro-bridged dimer [{Ru(η3:η3-C10H16)Cl(µ-Cl)}2]1 with a range of alkane- and arene-thiols in CH2Cl2 resulted in the formation of the simple, bridge-cleaved adducts [Ru(η3:η3-C10H16)Cl2(HSR)](R = Et 2, Me 3, Pri4, But5 or Ph 6). Reaction of 1 with an excess of thiol in methanol gave doubly thiolate-bridged compounds [{Ru(η3:η3-C10H16)Cl(µ-SR)}2](R = Et 7, Ph 12 or C6F513) each of which exists as two diastereoisomers but as a single geometrical isomer. In the case of 7 and 12 separation of the two diastereomeric forms proved possible because of their remarkably different solubilities in methanol, and their kinetic inertness. Reactions of 2 and 3 with 1 gave the mixed-bridge chloro/thiolato complexes [{Ru(η3:η3-C10H16)Cl}2(µ-Cl)(µ-SR)](R = Me 9 or Et 8). The unusual stereochemistry of these compounds is evident from analysis of their variable-temperature 1H NMR spectra. The crystal structure of 8 has been determined. Reaction of 1 with H2S in CH2Cl2 proceeds via the H2S adduct [Ru(η3:η3-C10H16)Cl2(SH2)]10, which rapidly reacts with further 1 with accompanying loss of HCl to give the singly SH-bridged complex [{Ru(η3:η3-C10H16)Cl}2(µ-Cl)(µ-SH)]11. Reaction of the EtSH compound 2 with a range of RuII and RhIII-containing compounds enabled the isolation of a number of unusual mixed-valence and mixed-metal complexes containing one or two bridging ethanethiolate ligands. The ruthenium(IV)–rhodium(III) compounds [(η3:η3-C10H16)ClRu(µ-Cl)(µ-SEt)RhCl(η5-C5Me5)] and [(η3:η3-C10H16)ClRu(η-SEt)2RhCl2(PMe2Ph)2] have been characterised by X-ray crystallography.

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