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)

The reactivity of [Pt2(μ-S)2(PPh3)4] towards [RuCl2(η6-arene)]2 (arene=C6H6, C6Me6, p-MeC6H4Pri=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)4ML]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)4Ru(CO)3Cl]+.