Fast CO2 hydrogenation to formic acid catalyzed by an Ir(PSiP) pincer hydride in a DMSO/water/ionic liquid solvent system
| Autor: | Muhammad I. Qadir, Marta Martín, Eduardo Sola, Jairton Dupont, Rodrigo Webber, Elizabeth Suárez |
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| Přispěvatelé: | Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Brasil), Conselho Nacional de Desenvolvimento Científico e Tecnológico (Brasil), Ministerio de Economía y Competitividad (España), Gobierno de Aragón, European Commission |
| Rok vydání: | 2020 |
| Předmět: |
Solvent system
010405 organic chemistry Hydride Formic acid Process Chemistry and Technology CO2 hydrogenation chemistry.chemical_element General Chemistry 010402 general chemistry Iridium 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences Pincer movement Ionic liquids chemistry.chemical_compound chemistry Ionic liquid Solvent-cage Gas composition |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname Catalysis Communications |
| Popis: | Complex [IrClH{κP,P,Si-Si(Me)(C6H4–2-PiPr2)2}] (1) showed a remarkable catalytic activity for CO2 hydrogenation in a DMSO/H2O solvent system incorporating 1,2-dimethyl-3-butylimidazolium acetate ionic liquid (IL), producing 0.94 M formic acid with initial TOFs up to 1432 h−1 (CO2/H2 = 20/40 bar, 30 °C). While the hydrogenation outcome followed dependences upon gas composition, pressure and temperature similar to those of other efficient systems in DMSO/H2O, the kinetic dependence upon catalyst loading revealed non-linear effects suggestive of relevant IL-catalyst interactions. NMR speciation studies identified two major complexes, [Ir(OCHO)(H){κP,P,Si-Si(Me)(C6H4–2-PiPr2)2}] (2) and [Ir(H)2{κP,P,Si-Si(Me)(C6H4–2-PiPr2)2}(DMSO)] (3), potentially responsible for catalytic cycling though inactive outside the current solvent system. The authors are thankful for financial support from CAPES (158804/2017-01 and 001), FAPERGS (16/2552-0000 and 18/2551-0000561-4), CNPq (406260/2018-4, 406750/2016-5 and 465454/2014-3), MINECO/Fondo Europeo de Desarrollo Regional (CTQ2015-64486-R) and Gobierno de Aragón/FEDER (E08-17R). E. Suárez is grateful to MINECO for a FPI fellowship (BES2013-063359). M. I. Qadir also acknowledges support from the European Union‘s Horizon 2020 research and innovation program under grant agreement no. 810310, which corresponds to the J. Heyrovsky Chair project (“ERA Chair at J. Heyrovský Institute of Physical Chemistry AS CR–The institutional approach towards ERA”) during the finalization of the paper. |
| Databáze: | OpenAIRE |
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