Resumen: 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.
Idioma: Inglés
DOI: 10.1021/acs.inorgchem.6b01216
Año: 2016
Publicado en: Inorganic Chemistry 55, 14 (2016), 7176-7181
ISSN: 0020-1669

Factor impacto JCR: 4.857 (2016)
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 4 / 46 = 0.087 (2016) - Q1 - T1
Factor impacto SCIMAGO: 1.804 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E35
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDC
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-53662-P
Tipo y forma: Artículo (PostPrint)

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