A manganese(V)-oxo π-cation radical complex: Influence of one-electron oxidation on oxygen-atom transfer

Katharine A. Prokop; Heather M. Neu; Sam P. de Visser; David P. Goldberg

doi:10.1021/ja2066237

A manganese(V)-oxo π-cation radical complex: Influence of one-electron oxidation on oxygen-atom transfer

Katharine A. Prokop, Heather M. Neu, Sam P. de Visser, David P. Goldberg

CE - Academic & Research

Research output: Contribution to journal › Article › peer-review

Abstract

One-electron oxidation of MnV–oxo corrolazine 2 affords 2+, the first example of a MnV(O) π-cation radical porphyrinoid complex, which was characterized by UV–vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2+ allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh3 and RSR substrates, and 2+ was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2+ and 2 and indicates that the greater electrophilicity of 2+ likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.

Original language	English
Pages (from-to)	15874–15877
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	40
Early online date	16 Sept 2011
DOIs	https://doi.org/10.1021/ja2066237
Publication status	Published - 12 Oct 2011

Keywords

Electron paramagnetic resonance spectroscopy
oxidation
Pyrroles
reactivity
transition metals

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10.1021/ja2066237

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title = "A manganese(V)-oxo π-cation radical complex: Influence of one-electron oxidation on oxygen-atom transfer",

abstract = "One-electron oxidation of MnV–oxo corrolazine 2 affords 2+, the first example of a MnV(O) π-cation radical porphyrinoid complex, which was characterized by UV–vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2+ allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh3 and RSR substrates, and 2+ was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2+ and 2 and indicates that the greater electrophilicity of 2+ likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.",

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T2 - Influence of one-electron oxidation on oxygen-atom transfer

AU - Prokop, Katharine A.

AU - Neu, Heather M.

AU - de Visser, Sam P.

AU - Goldberg, David P.

N1 - cited By 34

PY - 2011/10/12

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N2 - One-electron oxidation of MnV–oxo corrolazine 2 affords 2+, the first example of a MnV(O) π-cation radical porphyrinoid complex, which was characterized by UV–vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2+ allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh3 and RSR substrates, and 2+ was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2+ and 2 and indicates that the greater electrophilicity of 2+ likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.

AB - One-electron oxidation of MnV–oxo corrolazine 2 affords 2+, the first example of a MnV(O) π-cation radical porphyrinoid complex, which was characterized by UV–vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2+ allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh3 and RSR substrates, and 2+ was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2+ and 2 and indicates that the greater electrophilicity of 2+ likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.

KW - Electron paramagnetic resonance spectroscopy

KW - oxidation

KW - Pyrroles

KW - reactivity

KW - transition metals

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A manganese(V)-oxo π-cation radical complex: Influence of one-electron oxidation on oxygen-atom transfer

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Keywords

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