Coordination chemistry of the [Pt2(μ-S)2(PPh3)4] metalloligand with π-hydrocarbon derivatives of d6 ruthenium(II), osmium(II), rhodium(III) and iridium(III)

Abstract

The reactivity of [Pt2(μ-S)2 (PPh3)4] towards [RuCl2 (η6-arene)]2 (arene=C6 H6, C6Me6, p -MeC6 H4Pri = p-cymene), [OsCl2 (η6- p -cymene)]2 and [MCl2 (η5-C5Me5)]2 (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt2(μ-S)2(PPh3)4 ML]2+ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh4- or PF6- salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt2(μ-S)2 (PPh3)4] with RuClCp(PPh3) 2 (Cp=η5-C5H5) gives [Pt2(μ-S)2(PPh3) 4RuCp]+. In addition, the reaction of [Pt2(μ-S)2(PPh3)4] with the related carbonyl complex [RuCl2(CO)3] 2, monitored by electrospray mass spectrometry, gives [Pt2(μ-S)2(PPh3)4 Ru(CO)3Cl]+. © 2003 Elsevier B.V. All rights reserved.