doi:10.1021/acs.inorgchem.6b01216engEsteruelas, M. A.Nolis, P.Oliván, M.Oñate, E.Vallribera, A.Vélez, A.Ammonia Borane Dehydrogenation Promoted by a Pincer-Square-Planar Rhodium(I) Monohydride: A Stepwise Hydrogen Transfer from the Substrate to the CatalystART-2016-95915The 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.2016http://zaguan.unizar.es/record/7557810.1021/acs.inorgchem.6b01216http://zaguan.unizar.es/record/75578oai:zaguan.unizar.es:75578info:eu-repo/grantAgreement/ES/DGA/E35info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDCinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-Pinfo:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53662-PInorganic Chemistry 55, 14 (2016), 7176-7181All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess