Electronic structure of heterodinuclear complexes (bpy)2RuII(m-bpym)MLn; bpy = 2,2'-bipyridine; bpym = 2,2'-bipyrimidine; MLn = Cu(PPh3)2, Mo(CO)4, Re(CO)3Cl

, and . Inorganica Chimica Acta 181 (1): 15--21 (1991)


(Bpy)2Ru(m-bpym)Cu(PPh3)2(PF6)2 (bpy = 2,2'-bipyridine, bpym = 2,2'-bopyrimidine) and (bpy)2Ru(m-bypm)Mo(CO)4(PF6)2 were prepd. (Bpy)2Ru(m-bpym)MLn (MLn = Cu(PPh3)2, Mo(CO)4, Re(CO)3Cl) were studied by cyclic voltammetry, absorption spectroscopy, and by ESR of their singly reduced forms. Comparison with the homodinuclear analogs reveals that the metal-centered occupied d orbitals show relatively little change on coordination of a second metal (weak interaction) whereas the bpym-centered lowest unoccupied MOs p*1 and p*2 are stabilized by effects coming from both metal fragments. Combinations of metal fragments with different p donor/s acceptor characteristics give rise to variable charge transfer energies for major transitions d(Ru) $\rightarrow$ p*1, d(M) $\rightarrow$ p*1, d(Ru) $\rightarrow$ p*2; the appearance of spectra is further detd. by different widths and intensities of individual bands and by solvent dependence. on SciFinder(R)

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