Mn IV -Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn IV -oxo than Fe IV -oxo species
(2019) In Dalton Transactions 48(15). p.5007-5021- 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 Mn
II
and Mn
IV
-oxo complexes were generated and characterized. The [Mn
IV
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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.
- author
- Denler, Melissa C. ; Massie, Allyssa A. ; Singh, Reena LU ; Stewart-Jones, Eleanor ; Sinha, Arup LU ; Day, Victor W. ; Nordlander, Ebbe LU and Jackson, Timothy A.
- organization
- publishing date
- 2019
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Dalton Transactions
- volume
- 48
- issue
- 15
- pages
- 15 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- scopus:85064170452
- pmid:30916103
- ISSN
- 1477-9226
- DOI
- 10.1039/c9dt00308h
- language
- English
- LU publication?
- yes
- id
- 4958a518-d50f-4e87-87d8-2ca1b26c072d
- date added to LUP
- 2019-05-08 12:38:52
- date last changed
- 2024-06-11 10:22:30
@article{4958a518-d50f-4e87-87d8-2ca1b26c072d,
abstract = {{<p><br>
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 <br>
<sup>II</sup><br>
and Mn <br>
<sup>IV</sup><br>
-oxo complexes were generated and characterized. The [Mn <br>
<sup>IV</sup><br>
(O)(2pyN2B)] <br>
<sup>2+</sup><br>
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 <br>
<sup>IV</sup><br>
-oxo complexes with neutral, pentadentate N <br>
<sub>5</sub><br>
supporting ligands. The near-IR electronic absorption band maximum of [Mn <br>
<sup>IV</sup><br>
(O)(2pyN2B)] <br>
<sup>2+</sup><br>
, as well as DFT-computed metric parameters, are consistent with the equatorial (N-methyl)benzimidazolyl ligands being stronger donors to the Mn <br>
<sup>IV</sup><br>
center than the pyridyl and quinolinyl ligands found in analogous Mn <br>
<sup>IV</sup><br>
-oxo complexes. The hydrogen- and oxygen-atom transfer reactivities of [Mn <br>
<sup>IV</sup><br>
(O)(2pyN2B)] <br>
<sup>2+</sup><br>
were assessed through reactions with hydrocarbons and thioanisole, respectively. When compared with related Mn <br>
<sup>IV</sup><br>
-oxo adducts, [Mn <br>
<sup>IV</sup><br>
(O)(2pyN2B)] <br>
<sup>2+</sup><br>
showed muted reactivity in hydrogen-atom transfer reactions with hydrocarbons. This result stands in contrast to observations for the analogous Fe <br>
<sup>IV</sup><br>
-oxo complexes, where [Fe <br>
<sup>IV</sup><br>
(O)(2pyN2B)] <br>
<sup>2+</sup><br>
was found to be one of the more reactive members of its class. <br>
</p>}},
author = {{Denler, Melissa C. and Massie, Allyssa A. and Singh, Reena and Stewart-Jones, Eleanor and Sinha, Arup and Day, Victor W. and Nordlander, Ebbe and Jackson, Timothy A.}},
issn = {{1477-9226}},
language = {{eng}},
number = {{15}},
pages = {{5007--5021}},
publisher = {{Royal Society of Chemistry}},
series = {{Dalton Transactions}},
title = {{Mn
<sup>IV</sup>
-Oxo complex of a bis(benzimidazolyl)-containing N5 ligand reveals different reactivity trends for Mn
<sup>IV</sup>
-oxo than Fe
<sup>IV</sup>
-oxo species}},
url = {{http://dx.doi.org/10.1039/c9dt00308h}},
doi = {{10.1039/c9dt00308h}},
volume = {{48}},
year = {{2019}},
}