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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]
Copyright of Organometallics is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Unexpected Ccarbene−X (X: I, Br, Cl) Reductive Elimination from N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions.
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  Data: <searchLink fieldCode="JN" term="%22Organometallics%22">Organometallics</searchLink>. Sep2010, Vol. 29 Issue 17, p3683-3685. 3p.
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  Data: <searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Organocopper+compounds%22">Organocopper compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Carbenes%22">Carbenes</searchLink><br /><searchLink fieldCode="DE" term="%22Heterocyclic+compounds%22">Heterocyclic compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+halides%22">Metal halides</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation-reduction+reaction%22">Oxidation-reduction reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Elimination+reactions%22">Elimination reactions</searchLink>
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  Data: 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]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Organometallics is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/om1005726
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      – Code: eng
        Text: English
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      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Organocopper compounds
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      – SubjectFull: Carbenes
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      – SubjectFull: Heterocyclic compounds
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      – SubjectFull: Ligands (Chemistry)
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      – SubjectFull: Metal halides
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      – SubjectFull: Oxidation-reduction reaction
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      – SubjectFull: Elimination reactions
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      – TitleFull: Unexpected Ccarbene−X (X: I, Br, Cl) Reductive Elimination from N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions.
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            NameFull: Bo-Lin Lin
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              Text: Sep2010
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