Interplay between β-Diimino and β-Diketiminato Ligands in Nickel Complexes Active in the Proton Reduction Reaction
Two Ni complexes are reported with κ4-P2N2 β-diimino (BDI) ligands with the general formula [Ni(XBDI)](BF4)2, where BDI is N-(2-(diphenylphosphaneyl)ethyl)-4-((2-(diphenylphosphaneyl)ethyl)imino)pent-2-en-2-amine and X indicates the substituent in the α-carbon intradiimine position, X = H for 1(BF4)...
| Autores: | , , , , , |
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| Formato: | artículo |
| Fecha de publicación: | 2022 |
| País: | España |
| Recursos: | Universitat Autònoma de Barcelona |
| Repositorio: | Dipòsit Digital de Documents de la UAB |
| Idioma: | inglés |
| OAI Identifier: | oai:ddd.uab.cat:268092 |
| Acesso em linha: | https://ddd.uab.cat/record/268092 https://dx.doi.org/urn:doi:10.1021/acs.inorgchem.2c02150 |
| Access Level: | acceso abierto |
| Palavra-chave: | Complex 1 Electrochemical analysis General formulas Negatively charged Ni complexes Nickel complex NMR-spectroscopy Proton reduction Reduction reaction UV/ Vis spectroscopy |
| Resumo: | Two Ni complexes are reported with κ4-P2N2 β-diimino (BDI) ligands with the general formula [Ni(XBDI)](BF4)2, where BDI is N-(2-(diphenylphosphaneyl)ethyl)-4-((2-(diphenylphosphaneyl)ethyl)imino)pent-2-en-2-amine and X indicates the substituent in the α-carbon intradiimine position, X = H for 1(BF4)2 and X = Ph for 2(BF4)2. Electrochemical analysis together with UV-vis and NMR spectroscopy in acetonitrile and dimethylformamide (DMF) indicates the conversion of the β-diimino complexes 12+ and 22+ to the negatively charged β-diketiminato (BDK) analogues (1-H)+ and (2-H)+ via deprotonation in DMF. Moreover, further electrochemical and spectroscopy evidence indicates that the one-electron-reduced derivatives 1+ and 2+ can also rapidly evolve to the BDK (1-H)+ and (2-H)+, respectively, via hydrogen gas evolution through a bimolecular homolytic pathway. Finally, both complexes are demonstrated to be active for the proton reduction reaction in DMF at Eapp = -1.8 V vs Fc+/0, being the active species the one-electron-reduced derivative 1-H and 2-H. |
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