title: Probing the stereo-electronic properties of cationic rhodium complexes bearing chiral diphosphine ligands by 103Rh NMR.
abstract: (103)Rh NMR represents a powerful tool to assess the global electronic and steric contribution of diphosphine ligands on [Rh(COD)(diphosphine)](+) complexes. In the case of DIOP, BINAP and MeDUPHOS, this approach proved to be more informative than classical CO-stretching frequency measurements. After validation, this method has been extended to a set of seven diphosphines. (103)Rh NMR measurements on [Rh(COD)(diphosphine)]PF(6) lead to the following order of donor properties: dppe > MeBPE > MeDUPHOS > dppb > DIOP > BINAP > Tol-BINAP. This trend has been validated by DFT in the case of DIOP, BINAP and MeDUPHOS. In conjunction, (31)P NMR chemical shift has been shown to reflect the ring constraints of the Rh-diphosphine scaffold. This contribution is a step towards a mechanistic investigation of the catalytic hydrogenation of unsaturated substrates by (103)Rh NMR and DFT.
authors.affiliation: CNRS, Laboratoire de Chimie de Coordination, 205, route de Narbonne, F-31077 Toulouse, France.
authors.forename: Amandine
authors.initials: A
authors.lastname: Fabrello
authors.forename: Chiara
authors.initials: C
authors.lastname: Dinoi
authors.forename: Lionel
authors.initials: L
authors.lastname: Perrin
authors.forename: Philippe
authors.initials: P
authors.lastname: Kalck
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.forename: Martine
authors.initials: M
authors.lastname: Urrutigoity
authors.forename: Odile
authors.initials: O
authors.lastname: Dechy-Cabaret
mesh_terms: D002412:Cations / Q000737:chemistry; D004583:Electrons; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000592:standards; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D012015:Reference Standards; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D002412:Cations; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D012238:Rhodium