The dihydridoiridium(III) complex [IrH2Cl(PiPr(3))(2)] as a molecular building block for unsymmetrical binuclear rhodium-iridium and iridium-iridium compounds

The title compound [IrH2Cl(PiPr(3))(2)] (3) reacts with the chloro-bridged dimers [RhCl(PiPr(3))(2)](2) (1) and [IrCl(C8H14)(PiPr(3))](2) (5) by cleav age of the Cl-bridges to give the unsymmetrical binuclear complexes 4 and 6 with Rh(mu -Cl)(2)Ir and Ir(mu -Cl)(2)Ir as the central building block. Th e reactions of 3 with the bis(cyclooctene) and (1,5-cyclooctadiene) compoun ds [MCl(C8H14)(2)](2) (7, 8) and [MCl(eta (4)-C8H12)](2) (9, 10) (M = Rh, I r) occur analogously and afford the rhodium(I)-iridium(III) and iridium(I)- iridium(III) complexes 11-14 in 70-80% yield. Treatment of [(eta (4)-C8H12) M(mu -Cl)(2)IrH2(PiPr(3))(2)] (13, 14) With phenylacetylene leads to the fo rmation of the substitution products [(eta (4)-C8H12)M(mu -Cl)(2)IrH(C equi valent to CPh)(PiPr(3))(2)] (15, 16) without changing the central molecular core. Similarly, the compound [(eta (4)-C8H12)Rh(mu -Br)(2)IrH(C equivalen t to CPh)(PiPr(3))(2)] (18) has been prepared; it was characterized by X-ra y crystallography.