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 [Pt-2(mu-S)(2)(PPh3)(4)] towards [RuCl2(eta(6)-arene)](2) (arene = C6H6, C6Me6, p-MeC6H4Pri = p-cymene), [OsCl2(eta(6)-p-cymene)](2) and [MCl2(eta(5)-C5Me5)](2) (M = Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt-2(mu-S)(2)(PPh3)(4)ML](2+) (L = pi-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 [Pt-2(mu-S)(2)(PPh3)(4)] with RuClCp(PPh3)(2) (CP = eta(5)-C5H5) gives [Pt-2(mu-S)(2)(PPh3)(4)RuCp](+). In addition, the reaction of [Pt-2(mu-S)(2)(PPh3)(4)] with the related carbonyl complex [RuCl2(CO)(3)](2), monitored by electrospray mass spectrometry, gives [Pt-2(mu-S)(2)(PPh3)(4)Ru(CO)(3)Cl](+). (C) 2003 Elsevier B.V. All rights reserved.