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Title

Ammonia borane dehydrogenation promoted by a pincer-square-planar rhodium(I) monohydride: a stepwise hydrogen transfer from the substrate to the catalyst

AuthorsEsteruelas, Miguel A. ; Nolis, Pau; Oliván, Montserrat ; Oñate, Enrique ; Vallribera, Adelina; Vélez, Andrea
KeywordsAmmonia-borane dehydrogenation
Rhodium
Hydride
DFT
Mechanism
Issue Date2016
PublisherAmerican Chemical Society
CitationInorganic Chemistry 55(14): 7176-7181 (2016)
AbstractThe 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.
Publisher version (URL)http://dx.doi.org/10.1021/acs.inorgchem.6b01216
URIhttp://hdl.handle.net/10261/135544
DOI10.1021/acs.inorgchem.6b01216
ISSN0020-1669
E-ISSN1520-510X
Appears in Collections:(ISQCH) Artículos
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