title: Enhanced π-backdonation from gold(I): isolation of original carbonyl and carbene complexes.
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.
authors.affiliation: Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier/CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse Cedex 09 (France).
authors.forename: Maximilian
authors.initials: M
authors.lastname: Joost
authors.forename: Laura
authors.initials: L
authors.lastname: Estévez
authors.forename: Sonia
authors.initials: S
authors.lastname: Mallet-Ladeira
authors.forename: Karinne
authors.initials: K
authors.lastname: Miqueu
authors.forename: Abderrahmane
authors.initials: A
authors.lastname: Amgoune
authors.forename: Didier
authors.initials: D
authors.lastname: Bourissou
keywords: carbenoids; carbonyl ligands; diphosphines; gold; π-backdonation