000130694 001__ 130694
000130694 005__ 20240130150402.0
000130694 0247_ $$2doi$$a10.1021/acs.inorgchem.1c00380
000130694 0248_ $$2sideral$$a127138
000130694 037__ $$aART-2021-127138
000130694 041__ $$aeng
000130694 100__ $$0(orcid)0000-0001-9815-9383$$aBabón, J.C.$$uUniversidad de Zaragoza
000130694 245__ $$aHydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
000130694 260__ $$c2021
000130694 5060_ $$aAccess copy available to the general public$$fUnrestricted
000130694 5203_ $$aThe hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{¿2-N, O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{¿2-N, O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford ¿1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the ¿1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the ¿1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile. © 2021 American Chemical Society.
000130694 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P
000130694 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000130694 590__ $$a5.436$$b2021
000130694 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 46 = 0.109$$c2021$$dQ1$$eT1
000130694 592__ $$a1.121$$b2021
000130694 593__ $$aInorganic Chemistry$$c2021$$dQ1
000130694 593__ $$aChemistry (miscellaneous)$$c2021$$dQ1
000130694 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000130694 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000130694 700__ $$0(orcid)0000-0001-7183-4975$$aLópez, A.M.$$uUniversidad de Zaragoza
000130694 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000130694 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000130694 773__ $$g60, 10 (2021), 7284-7296$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000130694 8564_ $$s2084067$$uhttps://zaguan.unizar.es/record/130694/files/texto_completo.pdf$$yVersión publicada
000130694 8564_ $$s2878723$$uhttps://zaguan.unizar.es/record/130694/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000130694 909CO $$ooai:zaguan.unizar.es:130694$$particulos$$pdriver
000130694 951__ $$a2024-01-30-14:08:30
000130694 980__ $$aARTICLE