期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 16, 页码 6472-6480出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja201760c
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资金
- Agence Nationale pour la Recherche [ANR-07-BLAN-0294-01]
- CNRS
- Region Haute Normandie
- Region Basse Normandie (Crunch interregional network)
- ERDF
- Agence Nationale de la Recherche (ANR) [ANR-07-BLAN-0294] Funding Source: Agence Nationale de la Recherche (ANR)
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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