New dinuclear face- and edge-sharing bioctahedral ruthenium compounds containing 1,2-bis(diphenylphosphanyloxy)ethane

Abstract

The bidentate diphosphinite ligand 1,2-bis(diphenylphosphanyloxy)ethane (L), Ph2P-O-(CH2)2-O-PPh2, can be sequentially incorporated into a series of dinuclear chloro-bridged ruthenium compounds using [RuCl2(DMSO)4] as a precursor to give the new bioctahedral compounds [Ru2(μ-Cl)3(DMSO) 3Cl(η2-L)] (1), [Ru2(μ-Cl) 3(DMSO)Cl(η2-L)2] (2) and [Ru 2Cl2(η2-L)2{η1- L(O)}2(μ-Cl)2] (3). Compound 3 contains two partially oxidised diphosphinite ligands that act in a monodentate manner. These compounds can also be obtained by direct reaction of [RuCl2(DMSO)4] with the appropriate stoichiometric amount of L but in the case of 3 (in which prolonged heating is necessary) the reaction affords two mononuclear compounds [RuCl2(η2-L)(Ph2POPPh2)] (7) and [RuCl(CO)(η2-L)(Ph2POCH2)] (8), with ligand fragments coordinated to the metal probably originating in metal-mediated disruptions of L. Reaction of 2 with the monodentate ligands PPh 3-n(OEt)n (n = 1-3) (L′) affords the dinuclear doubly chloro-bridged compound [Ru2(μ-Cl)2Cl 2(η2-L)2(L′)2] (4), the dinuclear triply chloro-bridged compound [{Ru(η2-L)(L′)} 2-(μ-Cl)3]Cl (5) and the mononuclear compound [RuCl2(η2-L)(L′)2] (6). The solid-state structures of 2 (transoid isomer), 5 (transoid isomer), 6, 7 and 8 are reported. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.