Remarkable Stabilization of a Ligand-Based Mixed-Valence State in the Metal-Based Mixed Valent(Ru2)~(II,III)M~(II),(mu3-O)(M=Co,Ni)Trinuclear Cluster Complexes

摘要

Two consecutive one-electron reductions of the mixed-metal trinuclear complexes[(Ru~(III))2M~(II)(mu3-O)(mu-CH3COO)6-(S)(bzpy)2]{(M=Co,S=H2O)and(M=Ni,S=N,N'-dimethylformamide);bzpy=4-benzoylpyridine} in aceto-nitrile give stable "double" mixed-valence states where both(Ru2)~(II,III)and(bzpy-)(bzpy)states coexist.Splitting of the ligand-based redox waves,(bzpy)2/(bzpy_)(bzpy)/(bzpy_)2,is 0.35 and 0.34 V for the Co and Ni complexes,respectively.