Halogenated triphenylgallium and -indium in frustrated Lewis pair activations and hydrogenation catalysis.

Autor: Xu M; Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5H 3H6., Possart J; Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28-30, 48149 Münster, Germany., Waked AE; Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5H 3H6., Roy J; Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5H 3H6., Uhl W; Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 28-30, 48149 Münster, Germany., Stephan DW; Department of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5H 3H6 dstephan@chem.utoronto.ca.
Jazyk: angličtina
Zdroj: Philosophical transactions. Series A, Mathematical, physical, and engineering sciences [Philos Trans A Math Phys Eng Sci] 2017 Aug 28; Vol. 375 (2101).
DOI: 10.1098/rsta.2017.0014
Abstrakt: The Lewis acids Ga(C 6 F 5 ) 3 , In(C 6 F 5 ) 3 and Ga(C 6 Cl 5 ) 3 are prepared and their Lewis acidity has been probed experimentally and computationally. The species Ga(C 6 F 5 ) 3 and In(C 6 F 5 ) 3 in conjunction with phosphine donors are shown to heterolytically split H 2 and catalyse the hydrogenation of an imine. In addition, frustrated Lewis pairs (FLPs) derived from Ga(C 6 F 5 ) 3 and In(C 6 F 5 ) 3 and phosphines react with diphenyldisulfide to phosphoniumgallates or indates of the form [ t Bu 3 PSPh][PhSE(C 6 F 5 ) 3 ] and [ t Bu 3 PSPh][(μ-SPh)(E(C 6 F 5 ) 3 ) 2 ] (E = Ga, In). The potential of the FLPs based on Ga(C 6 F 5 ) 3 , In(C 6 F 5 ) 3 and Ga(C 6 Cl 5 ) 3 and phosphines is also shown in reactions with phenylacetylene to give pure or mixtures of the products [ t Bu 3 PH][PhCCE(C 6 X 5 ) 3 ] and R 3 P(Ph)C=C(H)E(C 6 X 5 ) 3 A number of these species are crystallographically characterized. The implications for the use of these species in FLP chemistry are considered.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.
(© 2017 The Author(s).)
Databáze: MEDLINE
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