Mechanistic investigations of imine hydrogenation catalyzed by dinuclear iridium complexes

Chemistry : a European Journal
Marta MartínLuis A Oro

Abstract

Treatment of [Ir2(mu-H)(mu-Pz)2H3(NCMe)(PiPr3)2] (1) with one equivalent of HBF4 or [PhNH=CHPh]BF4 affords efficient catalysts for the homogeneous hydrogenation of N-benzylideneaniline. The reaction of 1 with HBF4 leads to the trihydride-dihydrogen complex [Ir2(mu-H)(mu-Pz)2H2(eta2-H2)(NCMe)(PiPr3)2]BF4 (2), which has been characterized by NMR spectroscopy and DFT calculations on a model complex. Complex 2 reacts with imines such as tBuN=CHPh or PhN=CHPh to afford amine complexes [Ir2(mu-H)(mu-Pz)2H2(NCMe){L}(PiPr3)2]BF4 (L = NH(tBu)CH2Ph, 3; NH(Ph)CH2Ph, 4) through a sequence of proton- and hydride-transfer steps. Dihydrogen partially displaces the amine ligand of 4 to form 2; this complements a possible catalytic cycle for the N-benzylideneaniline hydrogenation in which the amine-by-dihydrogen substitution is the turnover-determining step. The rates of ligand substitution in 4 and its analogues with labile ligands other than amine are dependent upon the nature of the leaving ligand and independent on the incoming ligand concentration, in agreement with dissociative substitutions. Water complex [Ir2(mu-H)(mu-Pz)2H2(NCMe)(OH2)(PiPr3)2]BF4 (7) hydrolyzes N-benzylideneaniline, which eventually affords the poor hydrogenation catal...Continue Reading

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Mar 15, 2006·Chemistry : a European Journal·Marta MartínLuis A Oro

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Citations

May 21, 2015·Chemical Communications : Chem Comm·Laura Rubio-PérezLuis A Oro
Feb 13, 2013·Chemistry : a European Journal·Beatriz CalvoLuis A Oro
Mar 15, 2006·Chemistry : a European Journal·Marta MartínLuis A Oro
Apr 23, 2013·Chemistry : a European Journal·Agnieszka BartoszewiczBelén Martín-Matute
Apr 29, 2009·Journal of the American Chemical Society·Frederic W PatureauJoost N H Reek
Nov 4, 2009·Inorganic Chemistry·Riccardo PelosoPierre Braunstein
Feb 19, 2011·Chemical Reviews·Massimiliano Delferro, Tobin J Marks

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