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Article Dans Une Revue Journal of the American Chemical Society Année : 2011

Ph2P(BH3)Li: from ditopicity to dual reactivity.

Résumé

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.

Domaines

Chimie organique
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Dates et versions

hal-00991604 , version 1 (15-05-2014)

Identifiants

Citer

Gabriella Barozzino Consiglio, Pierre Queval, Anne Harrison-Marchand, Alessandro Mordini, Jean-François Lohier, et al.. Ph2P(BH3)Li: from ditopicity to dual reactivity.. Journal of the American Chemical Society, 2011, 133 (16), pp.6472-6480. ⟨10.1021/ja201760c⟩. ⟨hal-00991604⟩
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