Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity
Abstract
The mononuclear Mn(IV)-oxo complex [MnIV(O)(N4py)]2+, where N4py is the pentadentate ligand N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine, we propose to attack C–H bonds by an excited-state reactivity pattern [Cho, K.-B.; Shaik, S.; Nam, W. J. Phys. Chem. Lett. 2012, 3, 2851-2856 (DOI: 10.1021/jz301241z)]. In this model, a 4E excited state is utilized to provide a lower-energy barrier for hydrogen-atom transfer. This proposal is intriguing, as it offers both a rationale for the relatively high hydrogen-atom-transfer reactivity of [MnIV(O)(N4py)]2+ and a guideline for creating more reactive complexes through ligand modification. Here we employ a combination of electronic absorption and variable-temperature magnetic circular dichroism (MCD) spectroscopy to experimentally evaluate this excited-state reactivity model. Using these spectroscopic methods, in conjunction with time-dependent density functional theory (TD-DFT) and complete-active space self-consistent-field calculations (CASSCF), we define the ligand-field and charge-transfer excited states of [MnIV(O)(N4py)]2+. Through a graphical analysis of the signs of the experimental C-term MCD signals, we unambiguously assign a low-energy MCD feature of [MnIV(O)(N4py)]2+ as the 4E excited state predicted to be involved in hydrogen-atom-transfer reactivity. The CASSCF calculations predict enhanced MnIII-oxyl character on the excited-state 4E surface, consistent with previous DFT calculations. Potential-energy surfaces, developed using the CASSCF methods, are used to determine how the energies andmore »
- Authors:
-
- Department of Chemistry and Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence, Kansas 66045, United States
- Publication Date:
- Research Org.:
- Univ. of Kansas, Lawrence, KS (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1332142
- Alternate Identifier(s):
- OSTI ID: 1334178
- Grant/Contract Number:
- SC0016359
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 47; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Leto, Domenick F., Massie, Allyssa A., Rice, Derek B., and Jackson, Timothy A. Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b08661.
Leto, Domenick F., Massie, Allyssa A., Rice, Derek B., & Jackson, Timothy A. Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity. United States. https://doi.org/10.1021/jacs.6b08661
Leto, Domenick F., Massie, Allyssa A., Rice, Derek B., and Jackson, Timothy A. Tue .
"Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity". United States. https://doi.org/10.1021/jacs.6b08661.
@article{osti_1332142,
title = {Spectroscopic and Computational Investigations of a Mononuclear Manganese(IV)-Oxo Complex Reveal Electronic Structure Contributions to Reactivity},
author = {Leto, Domenick F. and Massie, Allyssa A. and Rice, Derek B. and Jackson, Timothy A.},
abstractNote = {The mononuclear Mn(IV)-oxo complex [MnIV(O)(N4py)]2+, where N4py is the pentadentate ligand N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine, we propose to attack C–H bonds by an excited-state reactivity pattern [Cho, K.-B.; Shaik, S.; Nam, W. J. Phys. Chem. Lett. 2012, 3, 2851-2856 (DOI: 10.1021/jz301241z)]. In this model, a 4E excited state is utilized to provide a lower-energy barrier for hydrogen-atom transfer. This proposal is intriguing, as it offers both a rationale for the relatively high hydrogen-atom-transfer reactivity of [MnIV(O)(N4py)]2+ and a guideline for creating more reactive complexes through ligand modification. Here we employ a combination of electronic absorption and variable-temperature magnetic circular dichroism (MCD) spectroscopy to experimentally evaluate this excited-state reactivity model. Using these spectroscopic methods, in conjunction with time-dependent density functional theory (TD-DFT) and complete-active space self-consistent-field calculations (CASSCF), we define the ligand-field and charge-transfer excited states of [MnIV(O)(N4py)]2+. Through a graphical analysis of the signs of the experimental C-term MCD signals, we unambiguously assign a low-energy MCD feature of [MnIV(O)(N4py)]2+ as the 4E excited state predicted to be involved in hydrogen-atom-transfer reactivity. The CASSCF calculations predict enhanced MnIII-oxyl character on the excited-state 4E surface, consistent with previous DFT calculations. Potential-energy surfaces, developed using the CASSCF methods, are used to determine how the energies and wave functions of the ground and excited states evolved as a function of Mn=O distance. Furthermore, the unique insights into ground- and excited-state electronic structure offered by these spectroscopic and computational studies are harmonized with a thermodynamic model of hydrogen-atom-transfer reactivity, which predicts a correlation between transition-state barriers and driving force},
doi = {10.1021/jacs.6b08661},
journal = {Journal of the American Chemical Society},
number = 47,
volume = 138,
place = {United States},
year = {Tue Nov 15 00:00:00 EST 2016},
month = {Tue Nov 15 00:00:00 EST 2016}
}
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