Bonding and Structure of Copper Nitrenes


Article discussing research on the bonding and structure of copper nitrenes.

Creation Date: October 4, 2008
UNT College of Arts and Sciences
UNT Scholarly Works
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Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

Creator (Author):
Dinescu, Adriana

University of North Texas

Creator :
Kazi, Abul B.

University of North Texas; University of Arkansas at Pine Bluff

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
  • Creation: October 4, 2008

Article discussing research on the bonding and structure of copper nitrenes.

Department: Chemistry

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.

Physical Description:

6 p.

Keyword(s): copper nitrenes | bonding
Source: Inorganic Chemistry, 2008, Washington D.C.: American Chemical Society, pp. 10067-10072
UNT College of Arts and Sciences
UNT Scholarly Works
  • DOI: 10.1021/ic801337f |
  • ARK: ark:/67531/metadc77132
Resource Type: Article
Format: Text
Access: Public
Publication Title: Inorganic Chemistry
Volume: 47
Issue: 21
Page Start: 10067
Page End: 10072
Pages: 6
Peer Reviewed: Yes