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Issue 15, 2019
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MnIV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for MnIV-oxo than FeIV-oxo species

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Abstract

Using the pentadentate ligand (N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine, 2pyN2B), presenting two pyridyl and two (N-methyl)benzimidazolyl donor moieties in addition to a central tertiary amine, new MnII and MnIV-oxo complexes were generated and characterized. The [MnIV(O)(2pyN2B)]2+ complex showed spectroscopic signatures (i.e., electronic absorption band maxima and intensities, EPR signals, and Mn K-edge X-ray absorption edge and near-edge data) similar to those observed for other MnIV-oxo complexes with neutral, pentadentate N5 supporting ligands. The near-IR electronic absorption band maximum of [MnIV(O)(2pyN2B)]2+, as well as DFT-computed metric parameters, are consistent with the equatorial (N-methyl)benzimidazolyl ligands being stronger donors to the MnIV center than the pyridyl and quinolinyl ligands found in analogous MnIV-oxo complexes. The hydrogen- and oxygen-atom transfer reactivities of [MnIV(O)(2pyN2B)]2+ were assessed through reactions with hydrocarbons and thioanisole, respectively. When compared with related MnIV-oxo adducts, [MnIV(O)(2pyN2B)]2+ showed muted reactivity in hydrogen-atom transfer reactions with hydrocarbons. This result stands in contrast to observations for the analogous FeIV-oxo complexes, where [FeIV(O)(2pyN2B)]2+ was found to be one of the more reactive members of its class.

Graphical abstract: MnIV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for MnIV-oxo than FeIV-oxo species

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Publication details

The article was received on 22 Jan 2019, accepted on 15 Mar 2019 and first published on 27 Mar 2019


Article type: Paper
DOI: 10.1039/C9DT00308H
Dalton Trans., 2019,48, 5007-5021

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    MnIV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for MnIV-oxo than FeIV-oxo species

    M. C. Denler, A. A. Massie, R. Singh, E. Stewart-Jones, A. Sinha, V. W. Day, E. Nordlander and T. A. Jackson, Dalton Trans., 2019, 48, 5007
    DOI: 10.1039/C9DT00308H

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