期刊
CHEMICAL SCIENCE
卷 4, 期 7, 页码 2788-2796出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3sc50347j
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资金
- Estonian Science Foundation [9105]
- LGF
- FCI
- AvH
- DFG
- DFG-SNF Forschergruppe 1175
The frustrated Lewis pair-mediated reversible hydrogen activation is studied as a function of the electron-donor quality of a series of phosphines. The increasing acidity of the generated phosphonium species leads to a stepwise lowering of the temperature for the highly reversible H-2-activation and permits concrete classification for the first time. The influence of the acid strength on the metal-free hydrogenation of selected olefins is investigated by kinetic experiments and quantum chemical calculations. Detailed information for the rate-determining steps fully support our mechanistic model of a protonation step prior to hydride transfer. The rate of hydrogenation is strongly dependent on the electronic nature of the phosphine and of the acidity of the corresponding phosphonium cation. A careful balance of these two factors provides highly efficient metal-free hydrogenation catalysts. The provided findings are used to revise the reactivity of Lewis bases in the hydrogenation of imines, one of the most recognized applications of FLPs.
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