Some new rhodium(I)-iridium(III) complexes with bridging hydride and chloride ligands. Synthesis of compounds [L2Rh(.mu.-H)(.mu.-Cl)IrH2L'2] (L = PEt3 or L2 = diphos; L' = PEt3, P-iso-Pr3) and the x-ray crystal structure of [(PEt3)2Rh(.mu.-H)(.mu.-Cl)IrH2(PEt3)2]

The reaction of [IrHS(PEt3)2] with complexes containing the unit “RhClL2” (L = PEt, or L2 = diphos, Ph2PCH2CH2PPh2) give compounds [L2Rh(p-H)(p-C1)IrHz(PEt3)z]. The molecular structure of 8. (L = PEt,) was determined by X-ray diffraction: monoclinic, space group m1/c, Z = 4, (I = 11.507 (2) A, b = 15.974 (4) A, c = 19.198 (4) A, fi = 103.19 (4)O. The structure was solved by Patterson and Fourier methods using 4946 observed reflections (I L 341)) and refined to a conventional R = 0.059. The coordination around rhodium is distorted square planar, and that around iridium is distorted octahedral. The Rh-Ir distance is 2.898 (1) A, and the bridging chlorine atom is asymmetrically bonded to the two metals. The structural features of this complex are compared with those of a series of related mono- and binuclear complexes. The formation of the dichloro-bridged complex [(diph~s)Rh(p-Cl)~IrH~(P-i-Pr~)~] is also reported.