Mononuclear hydroxo-manganese(III) species can be found in many instances in nature, such as in the non-heme manganese lipoxygenase, where this unit is proposed to initiate a proton-coupled electron-transfer (PCET) during dioxygenation of poly-unsaturated fatty acids. Model systems with varying ligand structures can provide great insight into the reactivity of these complicated metalloenzymes; however, there are only a few synthesized Mn(III)-OH complexes reported in the literature capable of undergoing PCET. Our group has recently synthesized one such complex, [Mn(III)(OH)(dpaq)]<sup>+</sup>, with the Mn(III)-OH supported by a pentadentate N5 ligand. In the presented work, the role of the electronic structure of the model Mn(III)-OH complexes participating in PCET is evaluated using theoretical electronic structure methods. Furthermore, through a combined experimental and theoretical approach, the effects of the LUMO energy on reactivity is explored through systematic perturbations to the [Mn(III)(OH)(dpaq)]<sup>+</sup>.

Insights into Mn(III)-OH reactivity: Experimental and theoretical investigations into the role of electronic structure on hydrogen atom abstraction

251st National Meeting (2016)

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