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Publisher Summary This chapter discusses the electron-transfer reactions of polynuclear organotransition metal complexes. The chemistry of polynuclear organometallic complexes has become increasingly important, particularly in aiding the understanding of the relationship among structure, bonding, and reactivity. A great deal of effort has been devoted to the study of linked metallocene units to probe the redox properties of compounds containing two or more identical electron-transfer sites. The imido-bridged complexes are reduced in a reversible one-electron process. The monoanion (E = P), prepared by sodium naphthalenide reduction of the neutral compound and isolable as a sodium salt, has an electron spin resonance (ESR) spectrum consisting of 15 triplets. There is very little information available on the redox properties of organometallic clusters of the early transition metals. The trinuclear carbonyls and the mixed metal clusters undergo one-electron reduction. Theoretical studies have shown that the monocations of both biferrocene and bis(fulvalene)diiron show some delocalization; the latter is much more delocalized than the former.