168721 20260217214838.0 sideral 56379 ART-2005-56379 eng Bolano, Tamara (orcid)0000-0001-8977-6734 Hydride-alkenylcarbyne to alkenylcarbene transformation in bisphosphine-osmium complexes 2005 The 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. info:eu-repo/semantics/closedAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 7.419 2005 CHEMISTRY, MULTIDISCIPLINARY 6 / 123 = 0.049 2005 Q1 T1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Castarlenas, Ricardo (orcid)0000-0003-4460-8678 Esteruelas, Miguel A. Universidad de Zaragoza (orcid)0000-0002-4829-7590 Modrego, F. Javier Universidad de Zaragoza (orcid)0000-0002-9633-3285 Oñate, Enrique Universidad de Zaragoza (orcid)0000-0003-2094-719X 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 127 (2005), 11184-11195 J. Am. Chem. Soc. Journal of the American Chemical Society 0002-7863 366212 http://zaguan.unizar.es/record/168721/files/texto_completo.pdf Versión publicada 2901163 http://zaguan.unizar.es/record/168721/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:168721 articulos driver 2026-02-17-20:14:13 ARTICLE