title: Axial coordination of NHC ligands on dirhodium(II) complexes: generation of a new family of catalysts.
abstract: An efficient new methodology for the arylation of aldehydes is disclosed which uses dirhodium(II) catalysts and N-heterocyclic carbene (NHC) ligands. Complexes of Rh 2(OAc) 4 with one and two NHCs attached on the axial positions were successfully isolated, fully characterized, and used as catalysts in the reaction. The saturated monocomplex ((NHC 5)Rh 2(OAc) 4) 31 was shown to be the most active catalyst and was particularly efficient in the arylation of alkyl aldehydes. DFT calculations support participation of complexes with one axial NHC in the reaction as the catalysts active species and indicate that hydrogen bonds involving dirhodium unit, reactants, and solvent (alcohol) play an important role on the reaction mechanism.
authors.affiliation: CQFM and CQE, Departamento de Engenharia Química e Biológica, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais 1, Lisbon, Portugal.
authors.forename: Alexandre F
authors.initials: AF
authors.lastname: Trindade
authors.forename: Pedro M P
authors.initials: PM
authors.lastname: Gois
authors.forename: Luís F
authors.initials: LF
authors.lastname: Veiros
authors.forename: Vânia
authors.initials: V
authors.lastname: André
authors.forename: M Teresa
authors.initials: MT
authors.lastname: Duarte
authors.forename: Carlos A M
authors.initials: CA
authors.lastname: Afonso
authors.forename: Stephen
authors.initials: S
authors.lastname: Caddick
authors.forename: F Geoffrey N
authors.initials: FG
authors.lastname: Cloke