title: Interplay between cationic and neutral species in the rhodium-catalyzed hydroaminomethylation reaction.
abstract: The reactivity of [Rh(CO)(2){(R,R)-Ph-BPE}]BF(4) (2) toward amine, CO and/or H(2) was examined by high-pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)(3) {(R,R)-Ph-BPE}]BF(4) (4) and [Rh(CO)(2)(NHC(5)H(10)){(R,R)-Ph-BPE}]BF(4) (8) were identified. The transformation of 2 into the neutral complex [RhH(CO)(2){(R,R)-Ph-BPE}] (3) under hydroaminomethylation conditions (CO/H(2), amine) was investigated. The full mechanisms related to the formation of 3, 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)(2)(CO)(2){(R,R)-Ph-BPE}]BF(4) (6), resulting from the oxidative addition of H(2) on 2.
authors.affiliation: Laboratoire de Chimie de Coordination UPR CNRS 8241, Composante ENSIACET, Université de Toulouse UPS-INP-LCC, 4 allée Emile Monso BP 44362, 31030 Toulouse Cedex 4, France.
authors.forename: Delphine
authors.initials: D
authors.lastname: Crozet
authors.forename: Aitor
authors.initials: A
authors.lastname: Gual
authors.forename: David
authors.initials: D
authors.lastname: McKay
authors.forename: Chiara
authors.initials: C
authors.lastname: Dinoi
authors.forename: Cyril
authors.initials: C
authors.lastname: Godard
authors.forename: Martine
authors.initials: M
authors.lastname: Urrutigoïty
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Daran
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.forename: Carmen
authors.initials: C
authors.lastname: Claver
authors.forename: Philippe
authors.initials: P
authors.lastname: Kalck