Mechanistic investigations of imine hydrogenation catalyzed by cationic iridium complexes

Chemistry : a European Journal
Marta MartínLuis A Oro

Abstract

Complexes [IrH2(eta6-C6H6)(PiPr3)]BF4 (1) and [IrH2(NCMe)3(PiPr3)]BF4 (2) are catalyst precursors for homogeneous hydrogenation of N-benzylideneaniline under mild conditions. Precursor 1 generates the resting state [IrH2{eta5-(C6H5)NHCH2Ph}(PiPr3)]BF4 (3), while 2 gives rise to a mixture of [IrH{PhN=CH(C6H4)-kappaN,C}(NCMe)2(PiPr3)]BF4 (4) and [IrH{PhN=CH(C6H4)-kappaN,C}(NCMe)(NH2Ph)(PiPr3)]BF4 (5), in which the aniline ligand is derived from hydrolysis of the imine. The less hindered benzophenone imine forms the catalytically inactive, doubly cyclometalated compound [Ir{HN=CPh(C6H4)-kappaN,C}2(NH2CHPh2)(PiPr3)]BF4 (6). Hydrogenations with precursor 1 are fast and their reaction profiles are strongly dependent on solvent, concentrations, and temperature. Significant induction periods, minimized by addition of the amine hydrogenation product, are commonly observed. The catalytic rate law (THF) is rate = k[1][PhN=CHPh]p(H2). The results of selected stoichiometric reactions of potential catalytic intermediates exclude participation of the cyclometalated compounds [IrH{PhN=CH(C6H4)-kappaN,C}(S)2(PiPr3)]BF4 [S = acetonitrile (4), [D6]acetone (7), [D4]methanol (8)] in catalysis. Reactions between resting state 3 and D2 reveal a selec...Continue Reading

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Citations

Jun 23, 2016·Chemistry : a European Journal·Bugga BalakrishnaAnton Vidal-Ferran
Oct 24, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Eduardo MolinosAndrew S Weller
Aug 30, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Cameron JonesAndreas Stasch
Mar 15, 2006·Chemistry : a European Journal·Marta MartínLuis A Oro
Apr 23, 2013·Chemistry : a European Journal·Agnieszka BartoszewiczBelén Martín-Matute
Aug 8, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Abdollah NeshatJoseph A R Schmidt
Jul 5, 2013·Organic & Biomolecular Chemistry·Xi LuTonglei Li
May 21, 2014·Organic & Biomolecular Chemistry·Xi LuTonglei Li
May 21, 2010·Journal of the American Chemical Society·Rebeca ReguilloSylviane Sabo-Etienne
Apr 12, 2013·Organic Letters·José Luis Núñez-Rico, Anton Vidal-Ferran

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