Journal ArticleDOI
Frustrated Lewis pairs: metal-free hydrogen activation and more.
Douglas W. Stephan,Gerhard Erker +1 more
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TLDR
Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid/Lewis base adducts, but both the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available to carry out unusual reactions.Abstract:
Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid/Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramolecular combinations of bulky phosphines or amines with strongly electrophilic RB(C(6)F(5))(2) components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H(+)/H(-) pairs (stabilized for example, in the form of the respective phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogenation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alkenes, aldehydes, and a variety of other small molecules, including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chemistry.read more
Citations
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Journal ArticleDOI
Frustrated Lewis pair chemistry: development and perspectives.
Douglas W. Stephan,Gerhard Erker +1 more
TL;DR: The current state of this young but rapidly expanding field is outlined in this Review and the future directions for its broadening sphere of impact are considered.
Journal ArticleDOI
Ammonia-borane and related compounds as dihydrogen sources.
Journal ArticleDOI
Frustrated Lewis Pairs
TL;DR: The articulation of the notion of "frustrated Lewis pairs" (FLPs), which emerged from the discovery that H2 can be reversibly activated by combinations of sterically encumbered Lewis acids and bases, has prompted a great deal of recent activity in development of FLP catalysts for the hydrogenation of a range of organic substrates.
Journal ArticleDOI
Frustrated Lewis pairs: from concept to catalysis.
TL;DR: The most dramatic finding from FLP chemistry was the discovery that FLPs can activate H2, thus countering the long-existing dogma that metals are required for such activation, and the development of new metal-free catalytic processes are described.
Journal ArticleDOI
The broadening reach of frustrated Lewis pair chemistry
TL;DR: The surprising chemistry of so-called frustrated Lewis pairs (FLPs), which cannot form their natural complex together are reviewed, as well as efforts to extend this concept to asymmetric hydrogenations and its application to various chemical systems.
References
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Asymmetric Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo‐ and Stereoselective Hydrogenation of Ketones
Ryoji Noyori,Takeshi Ohkuma +1 more
TL;DR: The newly devised [RuCl(2)(phosphane)(2)(1,2-diamine)] complexes are excellent precatalysts for homogeneous hydrogenation of simple ketones which lack any functionality capable of interacting with the metal center.
Journal ArticleDOI
Reversible, Metal-Free Hydrogen Activation
TL;DR: The compound (C6H2Me3)2PH(C 6F4)BH(C6F5)2 (Me, methyl), which is derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H2 at temperatures above 100°C.
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