A variety of manganese-dependent enzymes utilize mid- and high-valent manganese centers to promote redox reactions with substrates. The function of these enzymes vary from defense against reactive oxygen species to production of dioxygen from water. In these enzymes, Mn-hydroxo, Mn-peroxo, and Mn-oxo species are commonly proposed as intermediates. These intermediates are involved in O-O cleavage and formation reactions, and in proton-coupled electron-transfer reactions (PCET) with substrates. In order to understand the fundamental properties and chemical reactivity of such mid- and high-valent manganese complexes, our lab has generated models of MnIII-hydroxo, MnIII-peroxo, and MnIV-oxo intermediates that are amenable to detailed structure-function studies. Tetraaza macrocyclic ligands, originally developed by Prof. Daryle Busch, have played a prominent role in these efforts. This talk will focus on the unique insights into the physical properties and chemical reactivity of Mn-oxo and Mn-peroxo complexes afforded by studies of Mn complexes with tetraaza macrocyclic ligands and will discuss how this work has inspired more recent investigations.

Geometric and electronic influences on the reactivity of Mn complexes with aza macrocyclic ligands and beyond

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