From the pioneering work of Taube, 1 electron-transfer reactions can be mechanistically categorized into either inner sphere or outer sphere processes. The most well-studied systems in either case typically involve one-electron changes. Redox processes involving transfers of a multiple number of electrons, especially between two metals, are much less prevalent and consequently less well understood. The most extensive studies on multiple electron changes have involved atom transfer processes.2 These are typically two electron-transfer reactions mediated by either a bridging halogen3•4 or a bridging oxo5 ligand. The consideration of a nitrido ligand as a bridging species in redox reactions has received little attention.6 In this regard, we initiated studies on the bridging capabilities of the nitrido complexes of metalloporphyrins. We report herein the first example of a reversible net three electron redox process mediated by nitrogen atom transfer.
Available at: http://works.bepress.com/l-woo/37/