☆ 4.8 Article

Ph2P(BH3)Li: From Ditopicity to Dual Reactivity

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2011)

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 16, 页码 6472-6480

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AMER CHEMICAL SOC
DOI: 10.1021/ja201760c

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Chemistry, Multidisciplinary

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  1. Agence Nationale pour la Recherche [ANR-07-BLAN-0294-01]
  2. CNRS
  3. Region Haute Normandie
  4. Region Basse Normandie (Crunch interregional network)
  5. ERDF
  6. Agence Nationale de la Recherche (ANR) [ANR-07-BLAN-0294] Funding Source: Agence Nationale de la Recherche (ANR)

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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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