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Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes |
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| Authors: | Dr Maximilian Joost Dr Laura Estévez Sonia Mallet‐Ladeira Dr Karinne Miqueu Dr Abderrahmane Amgoune Dr Didier Bourissou |
| Institution: | 1. Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France);2. Institut des Sciences Analytiques et de Physico‐Chimie pour l'Environnement et les Matériaux (UMR 5254), Equipe Chimie Physique, Université de Pau et des Pays de l'Adour, Hélioparc, 2 Avenue du Président Angot, 64053 Pau cedex 09 (France);3. Departamento de Química Física, Universidade de Vigo, Facultade de Química Lagoas‐Marcosende s/n, 36310 Vigo, Galicia (Spain);4. Institut de Chimie de Toulouse (FR 2599), 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France) |
| Abstract: | The specific electronic properties of bent o‐carborane diphosphine gold(I) fragments were exploited to obtain the first classical carbonyl complex of gold (DPCb)AuCO]+ (ν(CO)=2143 cm?1) and the diphenylcarbene complex (DPCb)Au(CPh2)]+, which is stabilized by the gold fragment rather than the carbene substituents. These two complexes were characterized by spectroscopic and crystallographic means. The (DPCb)Au]+ fragment plays a major role in their stability, as substantiated by DFT calculations. The bending induced by the diphosphine ligand substantially enhances π‐backdonation and thereby allows the isolation of carbonyl and carbene complexes featuring significant π‐bond character. |
| Keywords: | carbenoids carbonyl ligands diphosphines gold π ‐backdonation |