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The reduction paths of two series of inorganometallic Ru complexes, Ru(Cl)(E‘)(CO)2(iPr-DAB) (E‘ = SnPh3, PbPh3) and Ru(E)(E‘)(CO)2(iPr-DAB) (E = Me, GePh3, SnPh3, E‘ = SnPh3; E = E‘ = PbPh3), were studied by a series of spectroelectrochemical techniques. Reduction of the Cl complexes is a two-electron ECE process which directly affords the closed-shell five-coordinate anions [Ru(E‘)(CO)2(iPr-DAB)]- via transient radicals [Ru(E‘)(CO)2(iPr-DAB)]•. In the final step of the overall ECEC sequence at room temperature the five-coordinate anions attack the parent complexes, producing the dimers [Ru(E‘)(CO)2(iPr-DAB)]2. In contrast, the non-halide complexes are reversibly reduced to the radical anions [Ru(E)(E‘)(CO)2(iPr-DAB)]•- whose stability arises from the strength of the delocalized axial E−Ru−E‘ bond. Subsequent reduction of [Ru(E‘)(CO)2(iPr-DAB)]2 and [Ru(E)(E‘)(CO)2(iPr-DAB)]•- ultimately yields [Ru(E‘)(CO)2(iPr-DAB)]-. Reverse oxidation of the anions directly results in the recovery of the parent complex...

organometallics

Spectroelectrochemical (UV−Vis, IR, NMR, and EPR) Study of the Inorganometallic Complexes Ru(E)(E‘)(CO)2(iPr-DAB) (E = Cl, E‘ = SnPh3, PbPh3; E = Me, SnPh3, GePh3, E‘ = SnPh3; E = E‘ = PbPh3; iPr-DAB = 1,4-Diisopropyl-1,4-diaza-1,3-butadiene)