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Electronic effects of triarylphosphines in metal-free hydrogen activation: a kinetic and computational study

Content Provider	Royal Society of Chemistry (RSC)
Author	Tussing, Sebastian Leito, Ivo Paradies, Jan Greb, Lutz Schirmer, Birgitta Grimme, Stefan Oña-Burgos, Pascual Kaupmees, Karl Lõkov, Märt
Copyright Year	2013
Abstract	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 H2-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.
Starting Page	2788
Ending Page	2796
Page Count	9
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	4
Issue Number	7
Journal	Chemical Science
DOI	10.1039/c3sc50347j
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Hydrogen Phosphine Lewis Ion Hydride Acid catalysis Phosphonium Hydrogenation Quantum tunnelling
Content Type	Text
Resource Type	Article
Subject	Chemistry

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