DINUCLEAR DIPHOSPHINE-BRIDGED COMPLEXES OF RHODIUM, IRIDIUM, AND RUTHENIUM - SYNTHESIS AND STRUCTURE

The syntheses of 25 new dinuclear diphosphine-bridged complexes of rhodium, iridium, and ruthenium with the general formula (eta(n)-aryl)MCl2R2P(CxHy)nPR2M(eta(n)-aryl) are reported (eta(n)-aryl = eta5-C5Me5 (Cp*), eta6-C6Me6, (hmb)). These complexes are examples of a rare class of compounds. To establish whether a metal-metal interaction exists, X-ray structure analyses for the following compounds were carried out: (Cp*IrCl2)2 (mu-dmpe) (1), (CP*RhCl2)2(mu-dmpe) (2), [(eta6-C6Me6)RuCl2]2 (mu-dmpe) (3), (Cp*IrCl2)2 (mu-dmpm) (4), (Cp*IrCl2)2(mu-dmpbe) (7), and [(eta6-C6Me6)RuCl2]2 (mu-dmph) (23). A metal-metal interaction in the solid state can be ruled out. Also, the following hydrido complexes have been synthesized: [Cp*Ir(H)2]2-(mu-dmpe) (24) and [(eta6-C6Me6)Ru(H)2]2(mu-dmpe) (25). The main purpose for the syntheses of these types of complexes is the search for new routes of CH activation, the results of which will be reported in a forthcoming paper.