Ebbe Nordlander
Professor
Mn IV -Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn IV -oxo than Fe IV -oxo species
Author
Summary, in English
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 Mn
IV
-oxo complexes with neutral, pentadentate N
5
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 Mn
IV
center than the pyridyl and quinolinyl ligands found in analogous Mn
IV
-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.
Department/s
- Chemical Physics
Publishing year
2019
Language
English
Pages
5007-5021
Publication/Series
Dalton Transactions
Volume
48
Issue
15
Document type
Journal article
Publisher
Royal Society of Chemistry
Topic
- Chemical Sciences
Status
Published
ISBN/ISSN/Other
- ISSN: 1477-9226