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Alkali Metal Species in the Reversible Activation of H 2
Author(s) -
Xu Maotong,
Jupp Andrew R.,
Qu ZhengWang,
Stephan Douglas W.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201806849
Subject(s) - chemistry , carbanion , toluene , alkali metal , frustrated lewis pair , lewis acids and bases , scrambling , hydride , medicinal chemistry , solvent , activation barrier , metal , inorganic chemistry , white phosphorus , phosphorus , stereochemistry , crystallography , molecule , catalysis , organic chemistry , linguistics , philosophy
MP( t Bu) 2 (M=Li, Na, K), KH and KN(SiMe 3 ) 2 are shown to activate HD reversibly. In the case of MP( t Bu) 2 this leads to isotopic scrambling and the formation of H 2 , D 2 , H(D)P( t Bu) 2 and MH(D) in C 6 D 6 . In toluene, KP( t Bu) 2 reacts with H 2 but also leads to isotopic scrambling into the methyl groups of the solvent toluene. DFT calculations reveal that these systems effect H 2 activation via cooperative interactions with the Lewis acidic alkali metal and the basic phosphorus, carbanion, or hydride centres, mimicking frustrated Lewis pair (FLP) behaviour.