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Issue 6, 2017
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Ligand non-innocence and strong correlation in manganese superoxide dismutase mimics

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Abstract

We examine the 1-electron reduction of manganese porphyrin complexes Mn(III) porphyrin and Mn(III) TDE-2-ImP5+, which have attracted recent interest due to their properties as superoxide dismutase mimics. We perform a series of electronic structure calculations using the variational 2-electron reduced density matrix (2-RDM) method with a large [30,30] active space that represents a wavefunction with 1019 variables, as well as the more traditional complete active space self-consistent field (CASSCF) method with a [14,14] active space. We show that the larger 2-RDM calculation, intractable with CASSCF, is required to capture the full effects of electron correlation in the molecule and predict the non-innocence of the porphyrin ligand during the reduction. The CASSCF method predicts single-reference systems exhibiting a metal-centered reduction, but the 2-RDM method predicts a strongly correlated system exhibiting a ligand-centered reduction. Based on these results, we find that the porphyrin ligand is reduced rather than the manganese, and suggest that the electron correlation plays a role in driving the ligand non-innocence.

Graphical abstract: Ligand non-innocence and strong correlation in manganese superoxide dismutase mimics

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Publication details

The article was received on 04 Nov 2016, accepted on 11 Jan 2017 and first published on 26 Jan 2017


Article type: Paper
DOI: 10.1039/C6CP07563K
Citation: Phys. Chem. Chem. Phys., 2017,19, 4656-4660
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    Ligand non-innocence and strong correlation in manganese superoxide dismutase mimics

    A. R. McIsaac and D. A. Mazziotti, Phys. Chem. Chem. Phys., 2017, 19, 4656
    DOI: 10.1039/C6CP07563K

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