Gilbert M. Brown, Thomas Ray. Weaver, F. Keene
1976
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Influential Citations
78
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Journal
Inorganic Chemistry
Abstract
A series of diaminebis(2,2'-bipyridine) complexes of ruthenium(II), e.g., [Ru(bipy)2(en)]2+, has been prepared and the spectral and redox properties were investigated. The ethylenediamine and trans-1,2-diaminocyclohexane complexes undergo net four-electron oxidations, either chemically or electrochemically, giving the corresponding a,d-diimine complexes. The chemical and spectral properties of the cup'-diimine complexes are similar to those of [Ru(bipy)3]z+. Complexes containing 2-(aminomethyl)pyridine and 1,2-diamino-2-methyIpropane undergo net two-electron oxidations, in which the single CH2-NH2 linkage has undergone oxidative dehydrogenation to the imine. Electrochemical and titrimetric data (using Ce(1V)) in acetonitrile show that the diamine oxidative dehydrogenation reactions are initiated by oxidation of ruthenium(I1) to ruthenium(III), and that the reactions probably occur in a stepwise manner via monoimine intermediates.