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Bonding and structure of copper nitrenes
Thomas R Cundari1, Adriana Dinescu, Abul B Kazi
1Center for Advanced Scientific Computing and Modeling, Department of Chemistry, University of North Texas, Box 305070, Denton, Texas 76203-5070, USA. tomc@unt.edu
Inorganic Chemistry
|October 7, 2008
Summary
Computational studies explore terminal copper nitrenes, crucial intermediates in catalysis. Findings reveal a singlet ground state for these copper nitrene complexes, challenging previous assumptions and offering new insights into their electronic structure and bonding.
Area of Science:
- Organometallic Chemistry
- Computational Chemistry
- Catalysis
Background:
- Copper nitrenes are key intermediates in catalytic aziridination and C-H amination reactions.
- Structurally characterized terminal copper nitrenes remain elusive despite advances in metal-ligand multiply bonded complexes.
Purpose of the Study:
- To computationally investigate the electronic structure and properties of terminal copper nitrene complexes.
- To provide theoretical insights in anticipation of experimental characterization.
Main Methods:
- Density Functional Theory (DFT)
- Complete Active Space Self-Consistent-Field (CASSCF) electronic structure calculations
- Hybrid Quantum Mechanical/Molecular Mechanical (QM/MM) methods
Main Results:
- DFT suggests a triplet ground state, while CASSCF calculations indicate a singlet ground state with a small singlet-triplet energy gap.
- The ground-state singlet copper nitrene exhibits a multiconfigurational (biradical) character and a bent geometry.
- A closed-shell singlet state with potential multiple bonding in the copper-nitrene bond was identified.
Conclusions:
- The ground state of terminal copper nitrenes is likely a singlet, characterized by biradical features and a bent geometry.
- Computational methods reveal nuanced electronic structures, including the possibility of multiple bonding, which are critical for understanding copper nitrene reactivity.
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