ORGANOMETALLIC THIOL AND THIOLATO COMPLEXES OF RUTHENIUM(IV)

Reaction of the ruthenium(iv) chloro-bridged dimer [{Ru(eta3:eta3-C10H16)Cl(mu-Cl)}2] 1 with a range of alkane- and arene-thiols in CH2Cl2 resulted in the formation of the simple. bridge-cleaved adducts [Ru(eta3:eta3-C10H16)Cl2(HSR)] (R = Et2, Me3, Pr(i) 4, Bu(t) 5 or Ph6). Reaction of 1 with an excess of thiol in methanol gave doubly thiolate-bridged compounds [{Ru(eta3:eta3-C10H16)Cl(mu-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(eta3:eta3-C10H16)Cl}2(mu-Cl)(mu-SR)] 10, (R = Me 9 or Et 8). The unusual stereochemistry of these compounds is evident from analysis of their variable-temperature H-1 NMR spectra. The crystal structure of 8 has been determined. Reaction of 1 with H2S in CH2Cl2 proceeds via the H2S adduct [Ru(eta3:eta3-C10H16)Cl2(SH2)] 10, which rapidly reacts with further 1 with accompanying loss of HCl to give the singly SH-bridged complex [{Ru(eta:eta3-C10H16)Cl}2(mu-SH)] 11. Reaction of the EtSH compound 2 with a range of Ru(II) and Rh(III)-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 [(eta3:eta3-C10H16)ClRu(mu-Cl)(mu-SEt)RhCl(eta5-C5Me5)] and [(eta3:eta3-C10H16)ClRu(mu-SEt)2RhCl2(PMe2Ph)2] have been characterised by X-ray crystallography.