title: Theoretical study of rhodium(I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes.
abstract: Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.
authors.affiliation: Laboratoire de Chimie Théorique et Physico-Chimie, Moléculaire du CNRS (UMR 5624), Université de Pau et des Pays de L'Adour, Avenue de L'Université, BP 1155, 64013 Pau, France.
authors.forename: Karinne
authors.initials: K
authors.lastname: Miqueu
authors.forename: Emmanuelle
authors.initials: E
authors.lastname: Despagnet-Ayoub
authors.forename: Philip W
authors.initials: PW
authors.lastname: Dyer
authors.forename: Didier
authors.initials: D
authors.lastname: Bourissou
authors.forename: Guy
authors.initials: G
authors.lastname: Bertrand