000151292 001__ 151292
000151292 005__ 20251017144611.0
000151292 0247_ $$2doi$$a10.1021/acs.organomet.1c00621
000151292 0248_ $$2sideral$$a125997
000151292 037__ $$aART-2021-125997
000151292 041__ $$aeng
000151292 100__ $$0(orcid)0000-0002-3284-1053$$aBuil, María L.$$uUniversidad de Zaragoza
000151292 245__ $$aDissimilarity in the Chemical Behavior of Osmaoxazolium Salts and Osmaoxazoles: Two Different Aromatic Metalladiheterocycles
000151292 260__ $$c2021
000151292 5060_ $$aAccess copy available to the general public$$fUnrestricted
000151292 5203_ $$aThe preparation of aromatic hydride-osmaoxazolium and hydrideoxazole compounds is reported and their reactivity toward phenylacetylene investigated. Complex [OsH(OH)( CPh)(IPr)((PPr3)-Pr-i)]OTf (1; IPr = 1, 3-bis(2, 6-diisopropylphenyl)imidazolylidene, OTf = CF3SO3) reacts with acetonitrile and benzonitrile to give [OsH{kappa(2)-C, O-[C(Ph)NHC(R)O]}(NCR)(IPr)((PPr3)-Pr-i)]OTf (R = Me (2), Ph (3)) via amidate intermediates, which are generated by addition of the hydroxide ligand to the nitrile. In agreement with this, the addition of 2-phenylacetamide to acetonitrile solutions of 1 gives [OsH{kappa(2)-C, O-[C(Ph)NHC(CH2Ph)O]}(NCCH3)(IPr)((PPr3)-Pr-i)]OTf (4). The deprotonation of the osmaoxazolium ring of 2 and 4 leads to the oxazole derivatives OsH{kappa(2)-C, O-[C(Ph)NC-(R)O]}(IPr)((PPr3)-Pr-i) (R = Me (5), CH2Ph (6)). Complexes 2 and 4 add their Os-H and Os-C bonds to the C-C triple bond of phenylacetylene to afford [Os{eta(3)-C-3, kappa(1)-O-[CH2C(Ph)C(Ph)NHC(R)O]}(NCCH3)(2)(IPr)]OTf (R = Me (7), CH2Ph (8)), bearing a tridentate amide-N-functionalized allyl ligand, while complexes 5 and 6 undergo a vicarious nucleophilic substitution of the hydride at the metal center with the alkyne, via the compressed dihydride adduct intermediates OsH2(C CPh){kappa(2)-C, O[C(Ph)NC(R)O]}(IPr)((PPr3)-Pr-i) (R = Me (9), CH2Ph (10)), which reductively eliminate H-2 to yield the acetylide-osmaoxazoles Os(C CPh){kappa(2)-C, O-[C(Ph)NC(R)O]}(IPr)((PPr3)-Pr-i) (R = Me (11), CH2Ph (12)).
000151292 536__ $$9info:eu-repo/grantAgreement/ES/DGA/FEDER E06-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MICINN/RED2018-102387-T
000151292 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000151292 590__ $$a3.837$$b2021
000151292 591__ $$aCHEMISTRY, ORGANIC$$b15 / 56 = 0.268$$c2021$$dQ2$$eT1
000151292 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b12 / 46 = 0.261$$c2021$$dQ2$$eT1
000151292 592__ $$a0.994$$b2021
000151292 593__ $$aOrganic Chemistry$$c2021$$dQ1
000151292 593__ $$aInorganic Chemistry$$c2021$$dQ1
000151292 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000151292 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.
000151292 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000151292 700__ $$aPicazo, Nieves R.
000151292 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000151292 773__ $$g40, 24 (2021), 4150-4162$$pOrganometallics$$tOrganometallics$$x0276-7333
000151292 8564_ $$s3820645$$uhttps://zaguan.unizar.es/record/151292/files/texto_completo.pdf$$yVersión publicada
000151292 8564_ $$s2874110$$uhttps://zaguan.unizar.es/record/151292/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000151292 909CO $$ooai:zaguan.unizar.es:151292$$particulos$$pdriver
000151292 951__ $$a2025-10-17-14:17:44
000151292 980__ $$aARTICLE