000151341 001__ 151341
000151341 005__ 20250307114715.0
000151341 0247_ $$2doi$$a10.1021/acs.organomet.1c00176
000151341 0248_ $$2sideral$$a127131
000151341 037__ $$aART-2021-127131
000151341 041__ $$aeng
000151341 100__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000151341 245__ $$aRepercussion of a 1, 3-Hydrogen Shift in a Hydride-Osmium-Allenylidene Complex
000151341 260__ $$c2021
000151341 5060_ $$aAccess copy available to the general public$$fUnrestricted
000151341 5203_ $$aAn unusual 1, 3-hydrogen shift from the metal center to the Cß atom of the C3-chain of the allenylidene ligand in a hydride-osmium(II)-allenylidene complex is the beginning of several interesting transformations in the cumulene. The hydride-osmium(II)-allenylidene complex was prepared in two steps, starting from the tetrahydride dimer [(Os(H···H){¿3-P, O, P-[xant(PiPr2)2]})2(µ-Cl)2][BF4]2 (1). Complex 1 reacts with 1, 1-diphenyl-2-propyn-1-ol to give the hydride-osmium(II)-alkenylcarbyne [OsHCl(CCH-CPh2){¿3-P, O, P-[xant(PiPr2)2]}]BF4 (2), which yields OsHCl(-C-C-CPh2){¿3-P, O, P-[xant(PiPr2)2]} (3) by selective abstraction of the Cß-H hydrogen atom of the alkenylcarbyne ligand with KtBuO. Complex 3 is metastable. According to results of DFT calculations, the migration of the hydride ligand to the Cß atom of the cumulene has an activation energy too high to occur in a concerted manner. However, the migration can be catalyzed by water, alcohols, and aldehydes. The resulting alkenylcarbyne-osmium(0) intermediate is unstable and evolves into a 7:3 mixture of the hydride-osmium(II)-indenylidene OsHCl(-CIndPh){¿3-P, O, P-[xant(PiPr2)2]} (4) and the osmanaphthalene OsCl(C9H6Ph){¿3-P, O, P-[xant(PiPr2)2]} (5). Protonation of 4 with HBF4 leads to the elongated dihydrogen complex [OsCl(¿2-H2)(-CIndPh){¿3-P, O, P-[xant(PiPr2)2]}]BF4 (6), while the protonation of 5 regenerates 2. In contrast to 4, complex 6 evolves to a half-sandwich indenyl derivative, [Os(¿5-IndPh)H{¿3-P, O, P-[xant(PiPr2)2]}][BF4]Cl (7). Phenylacetylene also provokes the 1, 3-hydrogen shift in 3. However, it does not participate in the migration. In contrast to water, alcohols, and aldehydes, it stabilizes the resulting alkenylcarbyne to afford [Os(CCH-CPh2)(¿2-HCCPh){¿3-P, O, P-[xant(PiPr2)2]}]Cl (8).
000151341 536__ $$9info:eu-repo/grantAgreement/ES/DGA/FEDER E06-20R$$9info:eu-repo/grantAgreement/ES/DGA/LMP148-18$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
000151341 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000151341 590__ $$a3.837$$b2021
000151341 591__ $$aCHEMISTRY, ORGANIC$$b15 / 56 = 0.268$$c2021$$dQ2$$eT1
000151341 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b12 / 46 = 0.261$$c2021$$dQ2$$eT1
000151341 592__ $$a0.994$$b2021
000151341 593__ $$aOrganic Chemistry$$c2021$$dQ1
000151341 593__ $$aInorganic Chemistry$$c2021$$dQ1
000151341 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000151341 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000151341 700__ $$0(orcid)0000-0003-1341-7449$$aPaz, S.$$uUniversidad de Zaragoza
000151341 700__ $$0(orcid)0000-0003-1974-5507$$aVélez, A.$$uUniversidad de Zaragoza
000151341 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000151341 773__ $$g40, 10 (2021), 1523-1537$$pOrganometallics$$tOrganometallics$$x0276-7333
000151341 8564_ $$s2182446$$uhttps://zaguan.unizar.es/record/151341/files/texto_completo.pdf$$yVersión publicada
000151341 8564_ $$s2886582$$uhttps://zaguan.unizar.es/record/151341/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000151341 909CO $$ooai:zaguan.unizar.es:151341$$particulos$$pdriver
000151341 951__ $$a2025-03-07-09:32:37
000151341 980__ $$aARTICLE