56323 20200221144252.0 doi 10.1021/jacs.6b05825 sideral 95621 ART-2016-95621 eng (orcid)0000-0002-3284-1053 Buil, M.L. Universidad de Zaragoza Square-Planar Alkylidyne-Osmium and Five-Coordinate Alkylidene-Osmium Complexes: Controlling the Transformation from Hydride-Alkylidyne to Alkylidene 2016 Access copy available to the general public Unrestricted Square-planar alkylidyne and five-coordinate alkylidene mixed iPr3P–Os–IPr (IPr = 1, 3-bis(diisopropylphenyl)imidazolylidene) complexes have been discovered and characterized, and their formation has been rationalized. The cationic five-coordinate hydride-alkylidyne compounds [OsHX(=CPh)(IPr)(PiPr3)]OTf (X = Cl (1), F (4); OTf = CF3SO3) undergo deprotonation with KOtBu to afford the trans-halide-alkylidyne square-planar derivatives OsX(=CPh)(IPr)(PiPr3) (X = Cl (2), F (5)). Oxidative addition of the C(sp)–H bond of phenylacetylene and methyl propiolate along the Cl–Os–CPh axis of 2 with the hydrogen atom directed to the alkylidyne leads to alkynyl-cis-hydride-alkylidyne intermediates, which rapidly evolve into the five-coordinate alkylidene complexes Os(C=CR)Cl(-CHPh)(IPr)(PiPr3) (R = Ph (6), CO2Me (7)) as a consequence of the migration of the hydride from the metal center to the Ca atom of the alkylidyne. Oxidative addition of the C(sp)–H bond of methyl propiolate along the X–Os–CPh axis of 2 and 5 with the hydrogen atom directed to the halide gives the alkynyl-trans-hydride-alkylidyne derivatives OsH(C=CCO2Me)X(=CPh)(IPr)(PiPr3) (X = Cl (8), F (9)). Complex 8 evolves into 7. However, complex 9 containing the stronger p-donor fluoride is stable. The oxidative addition of HCl to 2 selectively yields the cis-hydride-alkylidyne compound OsHCl2(=CPh)(IPr)(PiPr3) (10), which is also stable. info:eu-repo/grantAgreement/ES/DGA/E35 info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDC info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-P info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 13.858 2016 CHEMISTRY, MULTIDISCIPLINARY 10 / 166 = 0.06 2016 Q1 T1 7.492 2016 Biochemistry 2016 Q1 Colloid and Surface Chemistry 2016 Q1 Chemistry (miscellaneous) 2016 Q1 Catalysis 2016 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion (orcid)0000-0001-7620-9618 Cardo, J.J.F. (orcid)0000-0002-4829-7590 Esteruelas, M.A. (orcid)0000-0003-2094-719X Oñate, E. 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 138, 30 (2016), 9720-9728 J. Am. Chem. Soc. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 0002-7863 1585259 http://zaguan.unizar.es/record/56323/files/texto_completo.pdf Versión publicada 117750 http://zaguan.unizar.es/record/56323/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:56323 articulos driver 2020-02-21-13:28:20 ARTICLE