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
-
- pmid:30916103
- scopus:85064170452
- 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
- 2024-09-03 18:20:43
@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}}, }