000112148 001__ 112148
000112148 005__ 20230519145449.0
000112148 0247_ $$2doi$$a10.1021/acs.organomet.1c00565
000112148 0248_ $$2sideral$$a126001
000112148 037__ $$aART-2021-126001
000112148 041__ $$aeng
000112148 100__ $$0(orcid)0000-0003-0597-3357$$aCancela, Lara$$uUniversidad de Zaragoza
000112148 245__ $$aAzolium Control of the Osmium-Promoted Aromatic C-H Bond Activation in 1, 3-Disubstituted Substrates
000112148 260__ $$c2021
000112148 5060_ $$aAccess copy available to the general public$$fUnrestricted
000112148 5203_ $$aThe hexahydride complex OsH6((PPr3)-Pr-i)(2) promotes the C-H bond activation of the 1, 3-disubstituted phenyl group of the [BF4](-) and [BPh4](-) salts of the cations 1-(3-(isoquinolin-1-yl)phenyl)-3-methylimidazolium and 1-(3-(isoquinolin-1-yl)phenyl)-3-meth-ylbenzimidazolium. The reactions selectively afford neutral and cationic trihydride-osmium(IV) derivatives bearing kappa(2)-C, N- or kappa(2)-C, C-chelating ligands, a cationic dihydride-osmium(IV) complex stabilized by a kappa(3)-C, C, N-pincer group, and a bimetallic hexahydride formed by two trihydride-osmium(IV) fragments. The metal centers of the hexahydride are separated by a bridging ligand, composed of kappa(2)-C, N- and kappa(2)-C, C-chelating moieties, which allows electronic communication between the metal centers. The wide variety of obtained compounds and the high selectivity observed in their formation is a consequence of the main role of the azolium group during the activation and of the existence of significant differences in behavior between the azolium groups. The azolium role is governed by the anion of the salt, whereas the azolium behavior depends upon its imidazolium or benzimidazolium nature. While [BF4](-) inhibits the azolium reactions, [BPh4](-) favors the azolium participation in the activation process. In contrast to benzimidazolylidene, the imidazolylidene resulting from the deprotonation of the imidazolium substituent coordinates in an abnormal fashion to direct the phenyl C-H bond activation to the 2-position. The hydride ligands of the cationic dihydride-osmium(IV) pincer complex display intense quantum mechanical exchange coupling. Furthermore, this salt is a red phosphorescent emitter upon photoexcitation and displays a noticeable catalytic activity for the dehydrogenation of 1-phenylethanol to acetophenone and of 1, 2-phenylenedimethanol to 1-isobenzofuranone. The bimetallic hexahydride shows catalytic synergism between the metals, in the dehydrogenation of 1, 2, 3, 4-tetrahydroisoquinoline and alcohols.
000112148 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/RED2018-102387-T
000112148 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000112148 590__ $$a3.837$$b2021
000112148 592__ $$a0.994$$b2021
000112148 591__ $$aCHEMISTRY, ORGANIC$$b15 / 57 = 0.263$$c2021$$dQ2$$eT1
000112148 593__ $$aOrganic Chemistry$$c2021$$dQ1
000112148 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b12 / 46 = 0.261$$c2021$$dQ2$$eT1
000112148 593__ $$aInorganic Chemistry$$c2021$$dQ1
000112148 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000112148 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.
000112148 700__ $$0(orcid)0000-0003-0381-0917$$aOlivan, Montserrat
000112148 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000112148 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000112148 773__ $$g40, 23 (2021), 3979-3991$$pOrganometallics$$tOrganometallics$$x0276-7333
000112148 8564_ $$s1859290$$uhttps://zaguan.unizar.es/record/112148/files/texto_completo.pdf$$yVersión publicada
000112148 8564_ $$s3152111$$uhttps://zaguan.unizar.es/record/112148/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000112148 909CO $$ooai:zaguan.unizar.es:112148$$particulos$$pdriver
000112148 951__ $$a2023-05-18-14:41:58
000112148 980__ $$aARTICLE