Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)‐Oxo Complexes

Massie, Allyssa A.; Denler, Melissa C.; Cardoso, Luísa Thiara; Walker, Ashlie N.; Hossain, M. Kamal; Day, Victor W.; Nordlander, Ebbe; Jackson, Timothy A.

doi:10.1002/ange.201612309

Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)‐Oxo Complexes

Journal Article · Thu Mar 16 00:00:00 EDT 2017 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201612309· OSTI ID:1401072

Massie, Allyssa A. ^[1]; Denler, Melissa C. ^[1]; Cardoso, Luísa Thiara ^[1]; Walker, Ashlie N. ^[1]; Hossain, M. Kamal ^[2]; Day, Victor W. ^[1]; Nordlander, Ebbe ^[2]; Jackson, Timothy A. ^[1]

Department of Chemistry University of Kansas Lawrence KS USA
Chemical Physics Department of Chemistry Lund University Box 124 22100 Lund Sweden

Abstract

Manganese(IV)‐oxo complexes are often invoked as intermediates in Mn‐catalyzed C−H bond activation reactions. While many synthetic Mn ^IV ‐oxo species are mild oxidants, other members of this class can attack strong C−H bonds. The basis for these reactivity differences is not well understood. Here we describe a series of Mn ^IV ‐oxo complexes with N5 pentadentate ligands that modulate the equatorial ligand field of the Mn ^IV center, as assessed by electronic absorption, electron paramagnetic resonance, and Mn K‐edge X‐ray absorption methods. Kinetic experiments show dramatic rate variations in hydrogen‐atom and oxygen‐atom transfer reactions, with faster rates corresponding to weaker equatorial ligand fields. For these Mn ^IV ‐oxo complexes, the rate enhancements are correlated with both 1) the energy of a low‐lying ⁴ E excited state, which has been postulated to be involved in a two‐state reactivity model, and 2) the Mn ^III/IV reduction potentials.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0016359

OSTI ID:: 1401072

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 15 Vol. 129; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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