000056323 001__ 56323
000056323 005__ 20200221144252.0
000056323 0247_ $$2doi$$a10.1021/jacs.6b05825
000056323 0248_ $$2sideral$$a95621
000056323 037__ $$aART-2016-95621
000056323 041__ $$aeng
000056323 100__ $$0(orcid)0000-0002-3284-1053$$aBuil, M.L.$$uUniversidad de Zaragoza
000056323 245__ $$aSquare-Planar Alkylidyne-Osmium and Five-Coordinate Alkylidene-Osmium Complexes: Controlling the Transformation from Hydride-Alkylidyne to Alkylidene
000056323 260__ $$c2016
000056323 5060_ $$aAccess copy available to the general public$$fUnrestricted
000056323 5203_ $$aSquare-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.
000056323 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E35$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-51912-REDC$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2014-52799-P
000056323 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000056323 590__ $$a13.858$$b2016
000056323 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b10 / 166 = 0.06$$c2016$$dQ1$$eT1
000056323 592__ $$a7.492$$b2016
000056323 593__ $$aBiochemistry$$c2016$$dQ1
000056323 593__ $$aColloid and Surface Chemistry$$c2016$$dQ1
000056323 593__ $$aChemistry (miscellaneous)$$c2016$$dQ1
000056323 593__ $$aCatalysis$$c2016$$dQ1
000056323 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000056323 700__ $$0(orcid)0000-0001-7620-9618$$aCardo, J.J.F.
000056323 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000056323 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000056323 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000056323 773__ $$g138, 30 (2016), 9720-9728$$pJ. Am. Chem. Soc.$$tJOURNAL OF THE AMERICAN CHEMICAL SOCIETY$$x0002-7863
000056323 8564_ $$s1585259$$uhttps://zaguan.unizar.es/record/56323/files/texto_completo.pdf$$yVersión publicada
000056323 8564_ $$s117750$$uhttps://zaguan.unizar.es/record/56323/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000056323 909CO $$ooai:zaguan.unizar.es:56323$$particulos$$pdriver
000056323 951__ $$a2020-02-21-13:28:20
000056323 980__ $$aARTICLE