Unexpected C(carbene)-X (X : I, Br, Cl) Reductive Elimination From N-Heterocyclic Carbene Copper Halide Complexes Under Oxidative Conditions
The non-innocent behaviors of NHC ligands have attracted wide attention due to their important implications for catalyst designs and reaction mechanisms. Herein, we report facile C(carbene)-halogen reductive eliminations from NHC copper halide complexes at RT under oxidative conditions. Density func...
| Veröffentlicht in: | Organometallics. - 1998. - 29(2010), 17 vom: 13. Sept., Seite 3683-3685 |
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| Weitere Verfasser: | , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2010
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| Zugriff auf das übergeordnete Werk: | Organometallics |
| Schlagworte: | Journal Article |
| Zusammenfassung: | The non-innocent behaviors of NHC ligands have attracted wide attention due to their important implications for catalyst designs and reaction mechanisms. Herein, we report facile C(carbene)-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) to Cu(III) species followed by C(carbene)-halogen reductive eliminations from NHC Cu(III) halide complexes. Remarkably short C(carbene)-chloride contacts and rare interactions between the chloride lone pair electrons and the C(carbene)p(π) orbital were found for the calculated NHC Cu(III) chlorides. The facile C(carbene)-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 |
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| Beschreibung: | Date Revised 21.03.2024 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 0276-7333 |