000108287 001__ 108287
000108287 005__ 20211115135503.0
000108287 0247_ $$2doi$$a10.1021/acs.organomet.0c00582
000108287 0248_ $$2sideral$$a121175
000108287 037__ $$aART-2020-121175
000108287 041__ $$aeng
000108287 100__ $$0(orcid)0000-0001-9815-9383$$aBabón, J.C.$$uUniversidad de Zaragoza
000108287 245__ $$aDihydroboration of Alkyl Nitriles Catalyzed by an Osmium-Polyhydride: Scope, Kinetics, and Mechanism
000108287 260__ $$c2020
000108287 5060_ $$aAccess copy available to the general public$$fUnrestricted
000108287 5203_ $$aComplex OsH6(PiPr3)2 is an efficient catalyst precursor for the addition of pinacolborane and catecholborane to the C-N triple bond of alkyl nitriles. In this way, a variety of N, N-diborylamines have been isolated and fully characterized, including 13 derivatives not described so far. The range of nitriles used is wide and comprises substrates having unfunctionalized linear and branched chains, and functionalized chains with methoxide, trifluoromethyl, aryl, pyridyl, benzoyl, or cyanide groups. Kinetic studies demonstrate that the overall process consists of two consecutive irreversible reactions: the catalytic metal-promoted monohydroboration of the nitrile to afford the borylimine and the metal-free stoichiometric hydroboration of the latter to give the diborylamine. The mechanism of the hydroboration has been established by combining the kinetic analysis of the catalysis, stoichiometric reactions, and DFT calculations. The rate-determining step of the catalysis is the insertion of the C-N triple bond of the nitrile into the Os-B bond of an osmium-s-borane intermediate and is regiodirected by the nucleophilicity of the nitrogen atom and the electrophilicity of the carbon atom of the nitrile.
000108287 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9info:eu-repo/grantAgreement/ES/DGA/LMP148-18$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-78205-P$$9info:eu-repo/grantAgreement/ES/MINECO/PID2019-106184GB-I00
000108287 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000108287 590__ $$a3.876$$b2020
000108287 591__ $$aCHEMISTRY, ORGANIC$$b13 / 57 = 0.228$$c2020$$dQ1$$eT1
000108287 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b11 / 45 = 0.244$$c2020$$dQ1$$eT1
000108287 592__ $$a1.231$$b2020
000108287 593__ $$aInorganic Chemistry$$c2020$$dQ1
000108287 593__ $$aPhysical and Theoretical Chemistry$$c2020$$dQ1
000108287 593__ $$aOrganic Chemistry$$c2020$$dQ1
000108287 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000108287 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000108287 700__ $$aFernández, I.
000108287 700__ $$0(orcid)0000-0001-7183-4975$$aLópez, A.M.$$uUniversidad de Zaragoza
000108287 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000108287 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000108287 773__ $$g39, 21 (2020), 3864-3872$$pOrganometallics$$tOrganometallics$$x0276-7333
000108287 8564_ $$s441756$$uhttps://zaguan.unizar.es/record/108287/files/texto_completo.pdf$$yPostprint
000108287 8564_ $$s1159187$$uhttps://zaguan.unizar.es/record/108287/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000108287 909CO $$ooai:zaguan.unizar.es:108287$$particulos$$pdriver
000108287 951__ $$a2021-11-15-08:53:10
000108287 980__ $$aARTICLE