1228216-70-3Relevant academic research and scientific papers
Unexpected Ccarbene-X (X: I, Br, Cl) reductive elimination from N-heterocyclic carbene copper halide complexes under oxidative conditions
Lin, Bo-Lin,Kang, Peng,Stack, T. Daniel P.
scheme or table, p. 3683 - 3685 (2010/12/24)
The non-spectator roles of NHC ligands have attracted wide attention due to their important implications for reaction mechanisms and subsequent impact on catalyst design. Herein, we report facile Ccarbene-halogen reductive eliminations from NHC copper halide complexes at RT under oxidative conditions. Density functional calculations on a simplified model system suggest that the reactions occur through oxidation of Cu(I) species to Cu(III) species followed by Ccarbene-halogen reductive eliminations from NHC Cu(III) halide complexes. Remarkably short Ccarbene-chloride contacts and rare interactions between the chloride lone pair electrons and the C carbene pμ orbital were found for the calculated NHC Cu(III) chlorides. The facile Ccarbene-X reductive elimination reported here warrants consideration as a potential decomposition pathway in reactions involving NHC-supported high-valent metal complexes, especially with late transition metals.
