Facile synthesis of platinum based heterobimetallic carbonyl clusters from bis(1-alkenyl)Pt(II) precursors

A new route for the high yield synthesis of platinum containing mixed bimetallic carbonyl clusters of the type [PtRu2(CO)8L2] (where L2 = dppe, 1,2-bis(diphenylphosphino)ethane or dppp, 1,3-bis(diphenylphosphino)propane; L = PPh3) by the reaction of platinum-alkenyl [PtL2(1-alkenyl)2] precursors with [Ru3(CO)12] is reported. An unexpected multinuclear mixed cluster, [PtRu4(CO)13(μ4-PCH2CH2CH2PPh2)], obtained under prolonged refluxing conditions was also isolated. All the products were isolated and characterized by various spectroscopic and analytical techniques. In solution, the complex [PtRu2(CO)8(PPh3)2] gives [Pt2Ru(μ-CO)3(CO)2(PPh3)3] and Ru3(CO)11(PPh3). The structures and relative energies of intermediates and transition states in the proposed reaction mechanism for the {PtRu2} clusters have been investigated using density functional theory.