000102071 001__ 102071
000102071 005__ 20210902121759.0
000102071 0247_ $$2doi$$a10.1021/acs.organomet.0c00236
000102071 0248_ $$2sideral$$a118246
000102071 037__ $$aART-2020-118246
000102071 041__ $$aeng
000102071 100__ $$0(orcid)0000-0001-9815-9383$$aBabón, J.C.$$uUniversidad de Zaragoza
000102071 245__ $$aOsmium-Promoted Transformation of Alkyl Nitriles to Secondary Aliphatic Amines: Scope and Mechanism
000102071 260__ $$c2020
000102071 5060_ $$aAccess copy available to the general public$$fUnrestricted
000102071 5203_ $$aThe transformation of alkyl nitriles to symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6(PiPr3)2 (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-, and alkoxy-functionalized alkyl nitriles with linear or branched chains. The formation of the secondary amines involves primary imines, primary amines, and secondary imines as organic intermediates. The reactions take place under mild conditions (toluene, 100 °C, and 4 bar of H2). Stoichiometric reactions of 1 with pivalonitrile and 2-methoxyacetonitrile have allowed us to isolate the trihydride azavinylidene derivatives OsH3{=N=CHR}(PiPr3)2 (R = tBu (3), CH2OMe (4)). Their formation involves the insertion of the N-C triple bond of the substrates into an Os-H bond of the unsaturated tetrahydride OsH4(PiPr3)2 (A), which is generated by reductive elimination of H2 from the hexahydride precursor. The reaction of these trihydride azavinylidene species with H2 is the key step for the reduction of the N-C triple bond of the nitriles. In the absence of H2, the attack of A to the azavinylidene ligand produces the rupture of its C(sp2)-C(sp3) bond. As a consequence of this attack and the presence of primary imines and amines in the reaction media, the binuclear complexes (PiPr3)2H4Os(µ-CN)OsH3{¿1-N-(NH=CHCH2OMe)}(PiPr3)2 (5) and (PiPr3)2H4Os(µ-CN)OsH3{¿1-N-(NH2CH2CH2OMe)}(PiPr3)2 (6) have been isolated and characterized by X-ray diffraction analysis, for 2-methoxyacetonitrile. DFT calculations reveal noticeable similarities between the hydrogenations of nitriles to primary imines and those of primary imines to primary amines.
000102071 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9info:eu-repo/grantAgreement/ES/DGA/FEDER$$9info:eu-repo/grantAgreement/ES/DGA/FSE$$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
000102071 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000102071 590__ $$a3.876$$b2020
000102071 591__ $$aCHEMISTRY, ORGANIC$$b13 / 57 = 0.228$$c2020$$dQ1$$eT1
000102071 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b11 / 45 = 0.244$$c2020$$dQ1$$eT1
000102071 592__ $$a1.231$$b2020
000102071 593__ $$aInorganic Chemistry$$c2020$$dQ1
000102071 593__ $$aPhysical and Theoretical Chemistry$$c2020$$dQ1
000102071 593__ $$aOrganic Chemistry$$c2020$$dQ1
000102071 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000102071 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000102071 700__ $$0(orcid)0000-0001-7183-4975$$aLópez, A.M.$$uUniversidad de Zaragoza
000102071 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000102071 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000102071 773__ $$g39, 11 (2020), 2177–2188$$pOrganometallics$$tOrganometallics$$x0276-7333
000102071 8564_ $$s1833487$$uhttps://zaguan.unizar.es/record/102071/files/texto_completo.pdf$$yPostprint
000102071 8564_ $$s2913056$$uhttps://zaguan.unizar.es/record/102071/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000102071 909CO $$ooai:zaguan.unizar.es:102071$$particulos$$pdriver
000102071 951__ $$a2021-09-02-09:53:36
000102071 980__ $$aARTICLE