Turning the Tables: Ligand-Centered Hydride Shuttling in Organometallic BIP–Al Systems
The reversible storage and release of hydride equivalents remains a central challenge in the design of biomimetic redox systems. Cationic 2,6-bis(imino)pyridine organoaluminum complexes [(4-R-BIP)AlR2]+ (where R = H; R′ = Me, 1a; R′ = Et, 1b; R = Bn; R′ = Me, 1c) and their neutral 2,6-bis(imino)-4-R...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/176708 |
| Acceso en línea: | https://hdl.handle.net/11441/176708 https://doi.org/10.1021/acs.inorgchem.5c02587 |
| Access Level: | acceso abierto |
| Sumario: | The reversible storage and release of hydride equivalents remains a central challenge in the design of biomimetic redox systems. Cationic 2,6-bis(imino)pyridine organoaluminum complexes [(4-R-BIP)AlR2]+ (where R = H; R′ = Me, 1a; R′ = Et, 1b; R = Bn; R′ = Me, 1c) and their neutral 2,6-bis(imino)-4-R-dihydropyridinate counterparts [(4-R-HBIP)AlR2] 2a-c are presented as chemically reversible hydride exchangers. Interconversion between these systems is achieved through strong reducing agents such as M+[HBEt3]− (where M = Li; Na) or LiAlH4, while powerful electrophiles like B(C6F5)3 or cationic trityl salts Ph3C+ enable the reverse transformation, with the latter providing complete selectivity. Overall, this reversible hydride exchange mirrors natural NAD(P)H/NADP+ cofactor system. These findings establish a new platform for ligand-centered hydride shuttling, where the metal fragment acts as a passive modulator─inverting the traditional roles assigned to metal and ligand. |
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