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Unexpected Ccarbene−X (X: I, Br, Cl) Reductive Elimination from N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions.

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Title: Unexpected Ccarbene−X (X: I, Br, Cl) Reductive Elimination from N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions.
Authors: Bo-Lin Lin1, Peng Kang1, T. Daniel P. Stack1
Source: Organometallics. Sep2010, Vol. 29 Issue 17, p3683-3685. 3p.
Subjects: Metal complexes, Organocopper compounds, Carbenes, Heterocyclic compounds, Ligands (Chemistry), Metal halides, Oxidation-reduction reaction, Elimination reactions
Abstract: 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 Ccarbenepπorbital 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. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract: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 Ccarbenepπorbital 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. [ABSTRACT FROM AUTHOR]
ISSN:02767333
DOI:10.1021/om1005726