New Dinuclear Face‐ and Edge‐Sharing Bioctahedral Ruthenium Compounds Containing 1,2‐Bis(diphenylphosphanyloxy)ethane

The bidentate diphosphinite ligand 1,2‐bis(diphenylphosphanyloxy)ethane (L), Ph 2 P–O–(CH 2 ) 2 –O–PPh 2 , can be sequentially incorporated into a series of dinuclear chloro‐bridged ruthenium compounds using [RuCl 2 (DMSO) 4 ] as a precursor to give the new bioctahedral compounds [Ru 2 (μ‐Cl) 3 (DMSO) 3 Cl(η 2 ‐L)] ( 1 ), [Ru 2 (μ‐Cl) 3 (DMSO)Cl(η 2 ‐L) 2 ] ( 2 ) and [Ru 2 Cl 2 (η 2 ‐L) 2 {η 1 ‐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 [RuCl 2 (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 [RuCl 2 (η 2 ‐L)(Ph 2 POPPh 2 )] ( 7 ) and [RuCl(CO)(η 2 ‐L)(Ph 2 POCH 2 )] ( 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 [Ru 2 (μ‐Cl) 2 Cl 2 (η 2 ‐L) 2 (L′) 2 ] ( 4 ), the dinuclear triply chloro‐bridged compound [{Ru(η 2 ‐L)(L′)} 2 (μ‐Cl) 3 ]Cl ( 5 ) and the mononuclear compound [RuCl 2 (η 2 ‐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, 69451 Weinheim, Germany, 2006)