Dinuclear diphosphine-bridged complexes of rhodium, iridium, and ruthenium: Synthesis and structure

Article abstract of DOI:10.1021/om00020a025

The syntheses of 25 new dinuclear diphosphine-bridged complexes of rhodium, iridium, and ruthenium with the general formula (ηⁿ-aryl)MCl₂R₂P(C_xH _y)_nPR₂M(ηⁿ-aryl) are reported (ηⁿ-aryl = η⁵-C₅Me₅ (Cp*), η⁶-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 (μ-dmpe) (1), (Cp*RhCl₂)₂(μ-dmpe) (2), [(η⁶-C₆Me₆)RuCl₂]₂ (μ-dmpe) (3), (Cp*IrCl₂)₂(μ-dmpm) (4), (Cp*IrCl₂)₂(μ-dmpbe) (7), and [(η⁶-C₆Me₆)RuCl₂] ₂(μ-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-(μ-dmpe) (24) and [(η⁶-C₆Me₆)Ru(H)₂] ₂(μ-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.