Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst

Miguel A. Esteruelas, Pau Nolis, Montserrat Oliván, Enrique Oñate, Adelina Vallribera, Andrea Vélez

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43 Citations (Scopus)

Abstract

© 2016 American Chemical Society. The pincer d8-monohydride complex RhH{xant(PiPr2)2} (xant(PiPr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) promotes the release of 1 equiv of hydrogen from H3BNH3 and H3BNHMe2 with TOF50% values of 3150 and 1725 h-1, to afford [BH2NH2]n and [BH2NMe2]2 and the tandem ammonia borane dehydrogenation-cyclohexene hydrogenation. DFT calculations on the ammonia borane dehydrogenation suggest that the process takes place by means of cis-κ2-PP-species, through four stages including: (i) Shimoi-type coordination of ammonia borane, (ii) homolytic addition of the coordinated H-B bond to afford a five-coordinate dihydride-boryl-rhodium(III) intermediate, (iii) reductive intramolecular proton transfer from the NH3 group to one of the hydride ligands, and (iv) release of H2 from the resulting square-planar hydride dihydrogen rhodium(I) intermediate.
Original languageEnglish
Pages (from-to)7176-7181
JournalInorganic Chemistry
Volume55
Issue number14
DOIs
Publication statusPublished - 18 Jul 2016

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