Bioinspired mononuclear Mn complexes for O2 activation and biologically relevant reactions.

A general interest in harnessing the oxidizing power of dioxygen (O2) continues to motivate research efforts on bioinspired and biomimetic complexes to better understand how metalloenzymes mediate these reactions. The ubiquity of Fe- and Cu-based enzymes attracts significant attention and has resulted in many noteworthy developments for abiotic systems interested in direct O2 reduction and small molecule activation. However, despite the existence of Mn-based metalloenzymes with important O2-dependent activity, there has been comparatively less focus on the development of these analogues relative to Fe- and Cu-systems. In this Perspective, we summarize important contributions to the development of bioinspired mononuclear Mn complexes for O2 activation and studies on their reactivity, emphasizing important design parameters in the primary and secondary coordination spheres and outlining mechanistic trends.