Electro- and Photo-driven Reduction of CO 2 by a trans -(Cl)-[Os(diimine)(CO) 2 Cl 2 ] Precursor Catalyst: Influence of the Diimine Substituent and Activation Mode on CO/HCOO − Selectivity
| Autor: | Larisa Oresmaa, Jérôme Chauvin, Elina Laurila, Carmen E. Castillo, Sylvie Chardon-Noblat, Alain Deronzier, Matti Haukka, Jennifer Armstrong |
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| Přispěvatelé: | Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]) |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Dimer
Substituent 010402 general chemistry Photochemistry Electrocatalyst 01 natural sciences Catalysis photoinduced electron transfer Inorganic Chemistry chemistry.chemical_compound [CHIM.ANAL]Chemical Sciences/Analytical chemistry electrocatalysis Physical and Theoretical Chemistry ta116 Diimine ComputingMilieux_MISCELLANEOUS 010405 organic chemistry Chemistry Ligand Organic Chemistry osmium 0104 chemical sciences CO2 reduction Photocatalysis Selectivity photocatalysis |
| Zdroj: | ChemCatChem ChemCatChem, Wiley, 2016, 8 (16), pp.2667-2677. ⟨10.1002/cctc.201600539⟩ |
| ISSN: | 1867-3899 |
| DOI: | 10.1002/cctc.201600539⟩ |
| Popis: | A series of [OsII(NN)(CO)2Cl2] complexes where NN is a 2,2′-bipyridine ligand substituted in the 4,4′ positions by H (C1), CH3 (C2), C(CH3)3 (C3), or C(O)OCH(CH3)2 (C4) has been studied as catalysts for the reduction of CO2. Electrocatalysis shows that the selectivity of the reaction can be switched toward the production of CO or HCOO− with an electron-donating (C2, C3) or -withdrawing (C4) substituent, respectively. The electrocatalytic process is a result of the formation of an Os0-bonded polymer, which was characterized by electrochemistry, UV/Visible and EPR spectroscopies. Photolysis of the complexes under CO2 in DMF+TEOA produces CO as a major product with a remarkably stable turnover frequency during 14 h of irradiation. Our results suggest that electrocatalysis and photocatalysis occur through two distinct processes, starting mainly from an OsI dimer precatalyst if the reduction is performed by an electrode and an OsI mononuclear species in case of a photoreduction process. |
| Databáze: | OpenAIRE |
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