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  EPR/ENDOR and Theoretical Study of the Jahn–Teller-Active [HIPTN3N]MoVL Complexes (L = N, NH)

Sharma, A., Roemelt, M., Reithofer, M., Schrock, R. R., Hoffmann, B. M., & Neese, F. (2017). EPR/ENDOR and Theoretical Study of the Jahn–Teller-Active [HIPTN3N]MoVL Complexes (L = N, NH). Inorganic Chemistry, 56(12), 6906-6919. doi:10.1021/acs.inorgchem.7b00364.

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 Creators:
Sharma, Ajay1, Author
Roemelt, Michael2, 3, 4, Author              
Reithofer, Michael5, Author
Schrock, Richard R.5, Author
Hoffmann, Brian M.1, Author
Neese, Frank6, Author              
Affiliations:
1Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States, ou_persistent22              
2Max-Planck Institut für Chemische Energiekonversion, Stiftstrasse 34−36, D-45470 Mülheim an der Ruhr, Germany, ou_persistent22              
3Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, D-44780 Bochum, Germany, ou_persistent22              
4Research Group Roemelt, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_3018043              
5Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States, ou_persistent22              
6Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

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 Abstract: The molybdenum trisamidoamine (TAA) complex [Mo] {[3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2N]Mo} carries out catalytic reduction of N2 to ammonia (NH3) by protons and electrons at room temperature. A key intermediate in the proposed [Mo] nitrogen reduction cycle is nitridomolybdenum(VI), [Mo(VI)]N. The addition of [e/H+] to [Mo(VI)]N to generate [Mo(V)]NH might, in principle, follow one of three possible pathways: direct proton-coupled electron transfer; H+ first and then e; e and then H+. In this study, the paramagnetic Mo(V) intermediate {[Mo]N} and the [Mo]NH transfer product were generated by irradiating the diamagnetic [Mo]N and {[Mo]NH}+ Mo(VI) complexes, respectively, with γ-rays at 77 K, and their electronic and geometric structures were characterized by electron paramagnetic resonance and electron nuclear double resonance spectroscopies, combined with quantum-chemical computations. In combination with previous X-ray studies, this creates the rare situation in which each one of the four possible states of [e/H+] delivery has been characterized. Because of the degeneracy of the electronic ground states of both {[Mo(V)]N} and [Mo(V)]NH, only multireference-based methods such as the complete active-space self-consistent field (CASSCF) and related methods provide a qualitatively correct description of the electronic ground state and vibronic coupling. The molecular g values of {[Mo]N} and [Mo]NH exhibit large deviations from the free-electron value ge. Their actual values reflect the relative strengths of vibronic and spin–orbit coupling. In the course of the computational treatment, the utility and limitations of a formal two-state model that describes this competition between couplings are illustrated, and the implications of our results for the chemical reactivity of these states are discussed.

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Language(s): eng - English
 Dates: 2017-02-082017-06-012017-06-19
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.7b00364
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 56 (12) Sequence Number: - Start / End Page: 6906 - 6919 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669