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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents

ID: 734268.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
EPR/ENDOR and Theoretical Study of the Jahn-Teller-Active [HIPTN3N]MoVL Complexes (L = N- ,NH)
Authors:Sharma, Ajay; Roemelt, Michael; Reithofer, Michael; Schrock, Richard R.; Hoffman, Brian M.; Neese, Frank
Date of Publication (YYYY-MM-DD):2017
Title of Journal:Inorganic Chemistry
Journal Abbrev.:Inorg.Chem.
Issue / Number:12
Start Page:6906
End Page:6919
Review Status:Internal review
Audience:Experts Only
Abstract / Description:The molybdenum trisamidoamine (TAA) complex [Mo] {[3,5-(2,4,6-i-Pr3C6H2)(2)C6H3NCH2CH2N]Mo} carries out catalytic reduction of N-2 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(-); 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(V1) complexes, respectively, with gamma-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 vibtonic 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.
Comment of the Author/Creator:Date: 2017, JUN 19 2017
External Publication Status:published
Document Type:Article
Version Comment:Automatic journal name synchronization
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
Identifiers:ISI:000403973200019 [ID No:1]
ISSN:0020-1669 [ID No:2]
DOI:10.1021/acs.inorgchem.7b00364 [ID No:3]
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