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000131455 001__ 131455 000131455 005__ 20240319081011.0 000131455 0247_ $$2doi$$a10.1039/d2qi01056a 000131455 0248_ $$2sideral$$a130131 000131455 037__ $$aART-2022-130131 000131455 041__ $$aeng 000131455 100__ $$0(orcid)0000-0003-2249-6054$$aHermosilla, Pablo$$uUniversidad de Zaragoza 000131455 245__ $$aEfficient solventless dehydrogenation of formic acid by a CNC-based rhodium catalyst 000131455 260__ $$c2022 000131455 5060_ $$aAccess copy available to the general public$$fUnrestricted 000131455 5203_ $$aThe complex (CNC)MesRh(PMe2Ph)]PF6 (1) has been found to be an effective catalyst for solventless formic acid (FA) dehydrogenation, affording exclusively H2 and CO2 as decomposition products. The effect of the addition of a base as a co-catalyst was studied, and it was found that HCOONa was the most efficient additive in terms of catalyst efficiency with a catalyst loading of 0.016 mol%, reaching TOFmax values up to 5869 h-1. Additionally, we observed that the addition of water dramatically increased the catalytic activity in FA dehydrogenation, yielding TOFmax values up to 10 150 h-1. Additionally, VT kinetic NMR experiments allowed us to estimate the activation energy (¿G‡ = 18.12 ± 1.17 kcal mol-1) of the FA dehydrogenation catalysed by 1. Stoichiometric NMR experiments, aimed to shed light on the nature of possible catalytic intermediates, allowed us to detect and further isolate the RhIII hydrido formate complex (CNC)MesRh(¿O-OC(O)H)(PMe2Ph)H]PF6 (2), which originates from an oxidative addition of FA to 1; additionally, we could detect a bis(hydrido) RhIII complex (CNC)MesRh(PMe2Ph)H2]PF6 (1-H2), which is another operative intermediate in the catalytic FA dehydrogenation by 1. DFT calculations performed on the catalytic FA dehydrogenation perfectly accounted for the gathered experimental data; the approach of a FA molecule to 1 leads to O-H oxidative addition producing the ¿O-formate intermediate 2, which subsequently undergoes a FA-assisted isomerization to the ¿H-formate species. Further hydride abstraction generates the dihydrido intermediate 1-H2, which releases H2 upon interaction with another FA molecule closing the catalytic cycle. The rate-limiting step in the catalytic process corresponds to the hydride abstraction step, which agrees with the KIE values estimated by NMR experiments. © 2022 The Royal Society of Chemistry 000131455 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PGC2018-099383-B-I00$$9info:eu-repo/grantAgreement/ES/MICINN/RTI2018-099136-A-I00 000131455 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/ 000131455 590__ $$a7.0$$b2022 000131455 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b3 / 42 = 0.071$$c2022$$dQ1$$eT1 000131455 592__ $$a1.331$$b2022 000131455 593__ $$aInorganic Chemistry$$c2022$$dQ1 000131455 594__ $$a10.1$$b2022 000131455 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion 000131455 700__ $$0(orcid)0000-0001-9352-6922$$aUrriolabeitia, Asier$$uUniversidad de Zaragoza 000131455 700__ $$0(orcid)0000-0003-3144-5320$$aIglesias, Manuel 000131455 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, Victor$$uUniversidad de Zaragoza 000131455 700__ $$0(orcid)0000-0003-1707-3022$$aCasado, Miguel A.$$uUniversidad de Zaragoza 000131455 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000131455 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física 000131455 773__ $$g9, 17 (2022), 4538 [10 pp]$$pInorg. chem. front$$tInorganic Chemistry Frontiers$$x2052-1545 000131455 8564_ $$s541479$$uhttps://zaguan.unizar.es/record/131455/files/texto_completo.pdf$$yPostprint 000131455 8564_ $$s2548308$$uhttps://zaguan.unizar.es/record/131455/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint 000131455 909CO $$ooai:zaguan.unizar.es:131455$$particulos$$pdriver 000131455 951__ $$a2024-03-18-15:08:39 000131455 980__ $$aARTICLE
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