75578 20200221144215.0 doi 10.1021/acs.inorgchem.6b01216 sideral 95915 ART-2016-95915 eng (orcid)0000-0002-4829-7590 Esteruelas, M. A. Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the Catalyst 2016 Access copy available to the general public Unrestricted 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-¿2-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. info:eu-repo/grantAgreement/ES/DGA/E35 info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDC info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-P info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53662-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.857 2016 CHEMISTRY, INORGANIC & NUCLEAR 4 / 46 = 0.087 2016 Q1 T1 1.804 2016 Chemistry (miscellaneous) 2016 Q1 Physical and Theoretical Chemistry 2016 Q1 Inorganic Chemistry 2016 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Nolis, P. (orcid)0000-0003-0381-0917 Oliván, M. (orcid)0000-0003-2094-719X Oñate, E. Vallribera, A. (orcid)0000-0003-1974-5507 Vélez, A. 55, 14 (2016), 7176-7181 Inorg. chem. Inorganic Chemistry 0020-1669 379639 http://zaguan.unizar.es/record/75578/files/texto_completo.pdf Postprint 113935 http://zaguan.unizar.es/record/75578/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:75578 articulos driver 2020-02-21-13:12:53 ARTICLE