000168721 001__ 168721
000168721 005__ 20260217214838.0
000168721 0248_ $$2sideral$$a56379
000168721 037__ $$aART-2005-56379
000168721 041__ $$aeng
000168721 100__ $$0(orcid)0000-0001-8977-6734$$aBolano, Tamara
000168721 245__ $$aHydride-alkenylcarbyne to alkenylcarbene transformation in bisphosphine-osmium complexes
000168721 260__ $$c2005
000168721 5203_ $$aThe elongated dihydrogen complex (1) reacts with 1,1-diphenyl-2-propyn-1-ol and 2-methyl-3-butyn-2-ol to give the hydride-hydroxyvinylidene-π-alkynol derivatives [OsH{CCHC(OH)R2}{η2-HC⋮CC(OH)R2}(PiPr3)2]BF4 (R = Ph (2), Me (3)), where the π-alkynols act as four-electron donor ligands. Treatment of 2 and 3 with HBF4 and coordinating solvents leads to the dicationic hydride-alkenylcarbyne compounds [OsH(⋮CCHCR2)S2(PiPr3)2][BF4]2 (R = Ph, S = H2O (4), CH3CN (5); R = Me, S = CH3CN (6)), which in acetonitrile evolve into the alkenylcarbene complexes [Os(CHCHCR2)(CH3CN)3(PiPr3)2][BF4]2 (R = Ph (7), Me (8)) by means of a concerted 1,2-hydrogen shift from the osmium to the carbyne carbon atom. Treatment of 2-propanol solutions of 5 with NaCl affords OsHCl2(⋮CCHCPh2)(PiPr3)2 (10), which reacts with AgBF4 and acetonitrile to give [OsHCl(⋮CCHCPh2)(CH3CN)(PiPr3)2]BF4 (11). In this solvent complex 11 is converted to [OsCl(CHCHCPh2)(CH3CN)2(PiPr3)2]BF4 (12). Complex 5 reacts with CO to give [Os(CHCHCPh2)(CO)(CH3CN)2(PiPr3)2][BF4]2 (15). DFT calculations and kinetic studies for the hydride-alkenylcarbyne to alkenylcarbene transformation show that the difference of energy between the starting compounds and the transition states, which can be described as η2-carbene species increases with the basicity of the metallic center. The X-ray structures of 4 and 7 and the rotational barriers for the carbene ligands of 7, 8, and 12 are also reported.
000168721 540__ $$9info:eu-repo/semantics/closedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000168721 590__ $$a7.419$$b2005
000168721 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b6 / 123 = 0.049$$c2005$$dQ1$$eT1
000168721 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000168721 700__ $$0(orcid)0000-0003-4460-8678$$aCastarlenas, Ricardo
000168721 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.$$uUniversidad de Zaragoza
000168721 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F. Javier$$uUniversidad de Zaragoza
000168721 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique$$uUniversidad de Zaragoza
000168721 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000168721 773__ $$g127 (2005), 11184-11195$$pJ. Am. Chem. Soc.$$tJournal of the American Chemical Society$$x0002-7863
000168721 8564_ $$s366212$$uhttps://zaguan.unizar.es/record/168721/files/texto_completo.pdf$$yVersión publicada
000168721 8564_ $$s2901163$$uhttps://zaguan.unizar.es/record/168721/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000168721 909CO $$ooai:zaguan.unizar.es:168721$$particulos$$pdriver
000168721 951__ $$a2026-02-17-20:14:13
000168721 980__ $$aARTICLE