Manifestations of noninnocent ligand behavior.

The potential of redox-active ligands to behave "noninnocently" in transition-metal coordination compounds is reflected with respect to various aspects and situations. These include the question of establishing "correct" oxidation states, the identification and characterization of differently charged radical ligands, the listing of structural and other consequences of ligand redox reactions, and the distinction between barrierless delocalized "resonance" cases M(n)/L(n) ↔ M(n+1)L(n-1) versus separated valence tautomer equilibrium situations M(n)/L(n) ⇌ M(n+1)L(n-1). Further ambivalence arises for dinuclear systems with radical bridge M(n)(μ-L(•))M(n) versus mixed-valent alternatives M(n+1)(μ-L(-))M(n), for noninnocent ligand-bridged coordination compounds of higher nuclearity such as (μ(3)-L)M(3), (μ(4)-L)M(4), (μ-L)(4)M(4), or coordination polymers. Conversely, the presence of more than one noninnocently behaving ligand at a single transition-metal site in situations such as L(n)-M-L(n-1) or L(•)-M-L(•) may give rise to corresponding ligand-to-ligand interaction phenomena (charge transfer, electron hopping, and spin-spin coupling) and to redox-induced electron transfer with counterintuitive oxidation-state changes. The relationships of noninnocent ligand behavior with excited-state descriptions and perspectives regarding material properties and single-electron or multielectron reactivity are also illustrated briefly.