title: Ph2P(BH3)Li: from ditopicity to dual reactivity.
abstract: A multinuclear NMR study shows that the deprotonation of diphenylphosphine-borane by n-BuLi in THF leads to a disolvated lithium phosphido-borane Ph(2)P(BH(3))Li of which Li(+) is connected to the hydrides on the boron and two THF molecules rather than to the phosphorus. This entity behaves as both a phosphination and a reducing agent, depending on the kinetic or thermodynamic control imposed to the reaction medium. Density functional theory computations show that H(2)P(BH(3))Li exhibits a ditopic character (the lithium cation can be in the vicinity of the hydride or of the phosphorus). It explains its dual reactivity (H- or P-addition), both routes going through somewhat similar six-membered transition states with low activation barriers.
authors.affiliation: CNRS UMR 6014 & FR 3038, Université de Rouen and INSA de Rouen, 76821 Mont St Aignan Cedex, France.
authors.forename: Gabriella
authors.initials: G
authors.lastname: Barozzino Consiglio
authors.forename: Pierre
authors.initials: P
authors.lastname: Queval
authors.forename: Anne
authors.initials: A
authors.lastname: Harrison-Marchand
authors.forename: Alessandro
authors.initials: A
authors.lastname: Mordini
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Lohier
authors.forename: Olivier
authors.initials: O
authors.lastname: Delacroix
authors.forename: Annie-Claude
authors.initials: AC
authors.lastname: Gaumont
authors.forename: Hélène
authors.initials: H
authors.lastname: Gérard
authors.forename: Jacques
authors.initials: J
authors.lastname: Maddaluno
authors.forename: Hassan
authors.initials: H
authors.lastname: Oulyadi