Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes
Abstract
Abstract Manganese(IV)‐oxo complexes are often invoked as intermediates in Mn‐catalyzed C−H bond activation reactions. While many synthetic Mn IV ‐oxo species are mild oxidants, other members of this class can attack strong C−H bonds. The basis for these reactivity differences is not well understood. Here we describe a series of Mn IV ‐oxo complexes with N5 pentadentate ligands that modulate the equatorial ligand field of the Mn IV center, as assessed by electronic absorption, electron paramagnetic resonance, and Mn K‐edge X‐ray absorption methods. Kinetic experiments show dramatic rate variations in hydrogen‐atom and oxygen‐atom transfer reactions, with faster rates corresponding to weaker equatorial ligand fields. For these Mn IV ‐oxo complexes, the rate enhancements are correlated with both 1) the energy of a low‐lying 4 E excited state, which has been postulated to be involved in a two‐state reactivity model, and 2) the Mn III/IV reduction potentials.
- Authors:
-
- Univ. of Kansas, Lawrence, KS (United States)
- Lund Univ. (Sweden)
- Publication Date:
- Research Org.:
- Univ. of Kansas, Lawrence, KS (United States); Stanford Univ., CA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Institutes of Health (NIH); Ciências sem Fronteiras; National Science Foundation (NSF); European Commission (EC)
- OSTI Identifier:
- 1533097
- Alternate Identifier(s):
- OSTI ID: 1401075
- Grant/Contract Number:
- SC0016359; AC02-76SF00515; SC0012704; CHE-0946883
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 15; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; C-H activation; hydrogen atom transfer; kinetics; manganese; metal oxo compounds
Citation Formats
Massie, Allyssa A., Denler, Melissa C., Cardoso, Luísa Thiara, Walker, Ashlie N., Hossain, M. Kamal, Day, Victor W., Nordlander, Ebbe, and Jackson, Timothy A. Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes. United States: N. p., 2017.
Web. doi:10.1002/anie.201612309.
Massie, Allyssa A., Denler, Melissa C., Cardoso, Luísa Thiara, Walker, Ashlie N., Hossain, M. Kamal, Day, Victor W., Nordlander, Ebbe, & Jackson, Timothy A. Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes. United States. https://doi.org/10.1002/anie.201612309
Massie, Allyssa A., Denler, Melissa C., Cardoso, Luísa Thiara, Walker, Ashlie N., Hossain, M. Kamal, Day, Victor W., Nordlander, Ebbe, and Jackson, Timothy A. Thu .
"Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes". United States. https://doi.org/10.1002/anie.201612309. https://www.osti.gov/servlets/purl/1533097.
@article{osti_1533097,
title = {Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes},
author = {Massie, Allyssa A. and Denler, Melissa C. and Cardoso, Luísa Thiara and Walker, Ashlie N. and Hossain, M. Kamal and Day, Victor W. and Nordlander, Ebbe and Jackson, Timothy A.},
abstractNote = {Abstract Manganese(IV)‐oxo complexes are often invoked as intermediates in Mn‐catalyzed C−H bond activation reactions. While many synthetic Mn IV ‐oxo species are mild oxidants, other members of this class can attack strong C−H bonds. The basis for these reactivity differences is not well understood. Here we describe a series of Mn IV ‐oxo complexes with N5 pentadentate ligands that modulate the equatorial ligand field of the Mn IV center, as assessed by electronic absorption, electron paramagnetic resonance, and Mn K‐edge X‐ray absorption methods. Kinetic experiments show dramatic rate variations in hydrogen‐atom and oxygen‐atom transfer reactions, with faster rates corresponding to weaker equatorial ligand fields. For these Mn IV ‐oxo complexes, the rate enhancements are correlated with both 1) the energy of a low‐lying 4 E excited state, which has been postulated to be involved in a two‐state reactivity model, and 2) the Mn III/IV reduction potentials.},
doi = {10.1002/anie.201612309},
journal = {Angewandte Chemie (International Edition)},
number = 15,
volume = 56,
place = {United States},
year = {Thu Mar 16 00:00:00 EDT 2017},
month = {Thu Mar 16 00:00:00 EDT 2017}
}
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Works referencing / citing this record:
Oxidation of Naphthalene with a Manganese(IV) Bis(hydroxo) Complex in the Presence of Acid
journal, May 2018
- Jeong, Donghyun; Yan, James J.; Noh, Hyeonju
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Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant
journal, June 2018
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Structural Characterization of a Series of N5‐Ligated Mn IV ‐Oxo Species
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Oxidation of Naphthalene with a Manganese(IV) Bis(hydroxo) Complex in the Presence of Acid
journal, May 2018
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- Angewandte Chemie International Edition, Vol. 57, Issue 26
Crystallographic Evidence for a Sterically Induced Ferryl Tilt in a Non-Heme Oxoiron(IV) Complex that Makes it a Better Oxidant
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