Ph2P(BH3)Li: From Ditopicity to Dual Reactivity

Barozzino Consiglio, Gabriella;Queval, Pierre;Harrison-Marchand, Anne;Mordini, Alessandro;Oulyadi, Hassan;et.al.
(2011) Journal of the American chemical society — Vol. 133, n° 16, p. 6472-6480 (2011)

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Abstract
A multinuclear NMR study shows that the deprotonation of diphenylphosphine-borane by n-BuLi in THF leads to a disolvated lithium phosphido-borane Ph2P(BH3)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 H2P(BH3)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.
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Barozzino Consiglio, G., Queval, P., Harrison-Marchand, A., Mordini, A., Lohier, J.-F., Delacroix, O., Gaumont, A.-C., Gérard, H., Maddaluno, J., & Oulyadi, H. (2011). Ph2P(BH3)Li: From Ditopicity to Dual Reactivity. Journal of the American chemical society, 133(16), 6472-6480. https://doi.org/10.1021/ja201760c (Original work published 2011)