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

Denler, Melissa C.; Massie, Allyssa A.; Singh, Reena; Stewart-Jones, Eleanor; Sinha, Arup; Day, Victor W.; Nordlander, Ebbe; Jackson, Timothy A.

doi:10.1039/c9dt00308h

Mn^IV-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn^IV-oxo than Fe^IV-oxo species

Journal Article · Wed Mar 27 00:00:00 EDT 2019 · Dalton Transactions

DOI:https://doi.org/10.1039/c9dt00308h· OSTI ID:1612496

Denler, Melissa C. ^[1]; Massie, Allyssa A. ^[2]; Singh, Reena ^[3]; Stewart-Jones, Eleanor ^[2]; Sinha, Arup ^[3]; Day, Victor W. ^[2]; ^[3]; ^[2]

Univ. of Kansas, Lawrence, KS (United States); DOE/OSTI
Univ. of Kansas, Lawrence, KS (United States)
Lund Univ. (Sweden)

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 Mn^II and Mn^IV-oxo complexes were generated and characterized. The [Mn^IV(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 [Mn^IV(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 [Mn^IV(O)(2pyN2B)]²⁺ were assessed through reactions with hydrocarbons and thioanisole, respectively. When compared with related Mn^IV-oxo adducts, [Mn^IV(O)(2pyN2B)]²⁺ showed muted reactivity in hydrogen-atom transfer reactions with hydrocarbons. This result stands in contrast to observations for the analogous Fe^IV-oxo complexes, where [Fe^IV(O)(2pyN2B)]²⁺ was found to be one of the more reactive members of its class.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States); Stanford University, CA (United States); University of Kansas, Lawrence, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0012704; SC0016359

OSTI ID:: 1612496

Alternate ID(s):: OSTI ID: 1503397

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 15 Vol. 48; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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