Alkali Metal Species in the Reversible Activation of H2

MP(tBu)2 (M=Li, Na, K), KH and KN(SiMe3)2 are shown to activate HD reversibly. In the case of MP(tBu)2 this leads to isotopic scrambling and the formation of H2, D2, H(D)P(tBu)2 and MH(D) in C6D6. In toluene, KP(tBu)2 reacts with H2 but also leads to isotopic scrambling into the methyl groups of the...

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Published inAngewandte Chemie International Edition Vol. 57; no. 34; pp. 11050 - 11054
Main Authors Xu, Maotong, Jupp, Andrew R., Qu, Zheng‐Wang, Stephan, Douglas W.
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 20.08.2018
EditionInternational ed. in English
Subjects
Activation
Alkali metals
amides
frustrated Lewis pairs
H2 activation
Mimicry
phosphides
Phosphorus
Toluene
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Summary:MP(tBu)2 (M=Li, Na, K), KH and KN(SiMe3)2 are shown to activate HD reversibly. In the case of MP(tBu)2 this leads to isotopic scrambling and the formation of H2, D2, H(D)P(tBu)2 and MH(D) in C6D6. In toluene, KP(tBu)2 reacts with H2 but also leads to isotopic scrambling into the methyl groups of the solvent toluene. DFT calculations reveal that these systems effect H2 activation via cooperative interactions with the Lewis acidic alkali metal and the basic phosphorus, carbanion, or hydride centres, mimicking frustrated Lewis pair (FLP) behaviour. Mimicking frustration: MP(tBu)2 (M=Li, Na, K) and KN(SiMe3)2 activate HD reversibly. In toluene, KP(tBu)2 also reacts with H2 but leads to isotopic scrambling into the methyl groups of the solvent toluene. DFT calculations reveal that the mechanism mimics frustrated Lewis pair (FLP) behaviour.
Bibliography:Dedicated to Professor Richard Puddephatt on the occasion of his 75th birthday
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.201806849