000135485 001__ 135485
000135485 005__ 20260217205533.0
000135485 0247_ $$2doi$$a10.1021/acs.organomet.4c00064
000135485 0248_ $$2sideral$$a138640
000135485 037__ $$aART-2024-138640
000135485 041__ $$aeng
000135485 100__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.
000135485 245__ $$aDehydrogenation of Formic Acid Catalyzed by an Osmium-Polyhydride: relevance of Acid Assistance in the CO2 Formation Stage
000135485 260__ $$c2024
000135485 5060_ $$aAccess copy available to the general public$$fUnrestricted
000135485 5203_ $$aComplex OsH4{κ1-P,η2-GeH-[iPr2PCH(Me)CH2GeEt2H]}(PiPr3) (1) breaks down formic acid into H2 and CO2. The decomposition is catalytic with complex 1 being the main metallic species detected spectroscopically during the process. The kinetic analysis of the catalysis reveals that the decomposition rate is first order in the catalyst and independent of the concentration of formic acid, with the calculated activation parameters being: ΔH⧧ = 23 ± 2 kcal mol–1, ΔS⧧ = −1 ± 5 cal mol–1 K–1, and 298ΔG⧧ = 23 ± 3 kcal mol–1. Complex 1 also shows stoichiometric reactivity with benzoic and acetic acids. The reactions lead to OsH2{κ2-O,O-[O2CR]}{κ2-P,Ge-[iPr2PCH(Me)CH2GeEt2]}(PiPr3) (R = Ph (9), Me (10)). On the basis of these findings and DFT calculations, the following mechanism for the decomposition is proposed: complex 1 releases one molecule of H2 to produce an osmium(IV)-trihydride unsaturated intermediate, which promotes heterolytic activation of the O–H bond of formic acid. The metal fragment of the resulting osmium(IV)-(κ1-O-formate)-saturated derivative slides along the formate group, following the O–C–H pathway. The displacement is assisted externally by a molecule of formic acid and generates an osmium(IV)-(κ1-H-formate) species, which releases CO2 to regenerate 1 and close a cycle. The dissociation of H2 from the latter is the rate-determining step of catalysis.
000135485 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/RED2022-134287-T$$9info:eu-repo/grantAgreement/ES/MICINN/PRE2018-085398$$9info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/DGA/E06-23R
000135485 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000135485 590__ $$a2.9$$b2024
000135485 592__ $$a0.676$$b2024
000135485 591__ $$aCHEMISTRY, ORGANIC$$b14 / 57 = 0.246$$c2024$$dQ1$$eT1
000135485 593__ $$aInorganic Chemistry$$c2024$$dQ2
000135485 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b17 / 43 = 0.395$$c2024$$dQ2$$eT2
000135485 593__ $$aPhysical and Theoretical Chemistry$$c2024$$dQ2
000135485 593__ $$aOrganic Chemistry$$c2024$$dQ2
000135485 594__ $$a5.1$$b2024
000135485 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000135485 700__ $$0(orcid)0000-0001-7183-4975$$aLópez, Ana M.$$uUniversidad de Zaragoza
000135485 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000135485 700__ $$0(orcid)0000-0001-8609-7947$$aRaga, Esther
000135485 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000135485 773__ $$g43, 10 (2024), 1110–1118$$pOrganometallics$$tOrganometallics$$x0276-7333
000135485 8564_ $$s584082$$uhttps://zaguan.unizar.es/record/135485/files/texto_completo.pdf$$yPostprint
000135485 8564_ $$s1137269$$uhttps://zaguan.unizar.es/record/135485/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000135485 909CO $$ooai:zaguan.unizar.es:135485$$particulos$$pdriver
000135485 951__ $$a2026-02-17-20:33:18
000135485 980__ $$aARTICLE