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Article discussing research on the bonding and structure of copper nitrenes.
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6 p.
Notes
Reprinted with permission from Inorganic Chemistry. Copyright 2008 American Chemical Society.
Abstract: Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (ß-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S + 1) is the ground state, CASSCF calculations indicate the a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.
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Cundari, Thomas R., 1964- & Dinescu, Adriana.Bonding and Structure of Copper Nitrenes,
article,
October 4, 2008;
[Washington, D.C.].
(https://digital.library.unt.edu/ark:/67531/metadc77132/:
accessed September 26, 2023),
University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu;
crediting UNT College of Arts and Sciences.
