000078353 001__ 78353
000078353 005__ 20200811091508.0
000078353 0247_ $$2doi$$a10.1021/acs.organomet.7b00509
000078353 0248_ $$2sideral$$a105463
000078353 037__ $$aART-2018-105463
000078353 041__ $$aeng
000078353 100__ $$0(orcid)0000-0002-5465-4873$$aPuerta-Oteo, R.
000078353 245__ $$aExperimental and Theoretical Mechanistic Investigation on the Catalytic CO2 Hydrogenation to Formate by a Carboxylate-Functionalized Bis(N -heterocyclic carbene) Zwitterionic Iridium(I) Compound
000078353 260__ $$c2018
000078353 5060_ $$aAccess copy available to the general public$$fUnrestricted
000078353 5203_ $$aThe bis-imidazolium salt, 1, 1-bis(N-methylimidazolium) acetate bromide, is a convenient precursor for the synthesis of zwitterionic iridium(I) [Ir(cod){(MeIm)2CHCOO}] and cationic iridium(III) [IrH(cod){(MeIm)2CHCOO}]+ compounds (MeIm = 3-methylimidazol-2-yliden-1-yl) having a carboxylate-functionalized bis(NHC) ligand. The [Ir(cod){(MeIm)2CHCOO}] compound catalyzes the hydrogenation of CO2 to formate in water using NEt3 as base, reaching turnover numbers of approximately 1500. Reactivity studies have shown that activation of the catalyst precursor involves the reaction with H2 in a multistep process that under catalytic conditions results in the formation of a dihydrido iridium(III) octahedral [IrH2(H2O){(MeIm)2CHCOO}] species stabilized by the ¿3-C, C', O coordination of the ligand. DFT studies on the mechanism were carried out to elucidate two possible roles of the base. In the first one, NEt3 neutralizes only the produced formic acid, whereas in the second it assists the proton transfer in heterolytic cleavage of the H2 molecule. Although this base-involved mechanism is more favorable in that it exhibits a lower energy span for the overall reaction, the energy barrier obtained from kinetic experiments suggests that both mechanisms could be operative under the experimental reaction conditions.
000078353 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E07$$9info:eu-repo/grantAgreement/ES/MINECO/BES-2011-045364$$9info:eu-repo/grantAgreement/ES/MINECO/EEBB-I-14-08939$$9info:eu-repo/grantAgreement/ES/MINECO/EEBB-I-15-10125$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P
000078353 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000078353 590__ $$a4.1$$b2018
000078353 591__ $$aCHEMISTRY, ORGANIC$$b11 / 57 = 0.193$$c2018$$dQ1$$eT1
000078353 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 45 = 0.111$$c2018$$dQ1$$eT1
000078353 592__ $$a1.473$$b2018
000078353 593__ $$aInorganic Chemistry$$c2018$$dQ1
000078353 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000078353 593__ $$aOrganic Chemistry$$c2018$$dQ1
000078353 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000078353 700__ $$aHölscher, M.
000078353 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M.V.$$uUniversidad de Zaragoza
000078353 700__ $$aLeitner, W.
000078353 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, V.
000078353 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J.J.$$uUniversidad de Zaragoza
000078353 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000078353 773__ $$g37, 5 (2018), 684-696$$pOrganometallics$$tOrganometallics$$x0276-7333
000078353 8564_ $$s931407$$uhttps://zaguan.unizar.es/record/78353/files/texto_completo.pdf$$yPostprint
000078353 8564_ $$s123341$$uhttps://zaguan.unizar.es/record/78353/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000078353 909CO $$ooai:zaguan.unizar.es:78353$$particulos$$pdriver
000078353 951__ $$a2020-08-11-09:03:26
000078353 980__ $$aARTICLE