Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes
A diverse set of 2 e−/2 H+ reactions are described that interconvert [RuII(bpy)(en*)2]2+ and [RuIV(bpy)(en‐H*)2]2+ (bpy=2,2′‐bipyridine, en*=H2NCMe2CMe2NH2, en*‐H=H2NCMe2CMe2NH−), forming or cleaving different O−H, N−H, S−H, and C−H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3‐...
| Autores: | , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2017 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/43385 |
| Acceso en línea: | http://hdl.handle.net/11336/43385 |
| Access Level: | acceso abierto |
| Palabra clave: | Multiredox Proton-Coupled Electron Transfer (Pcet) Ruthenium Amido Multielectron Multiproton https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | A diverse set of 2 e−/2 H+ reactions are described that interconvert [RuII(bpy)(en*)2]2+ and [RuIV(bpy)(en‐H*)2]2+ (bpy=2,2′‐bipyridine, en*=H2NCMe2CMe2NH2, en*‐H=H2NCMe2CMe2NH−), forming or cleaving different O−H, N−H, S−H, and C−H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3‐cyclohexadiene. These proton‐coupled electron transfer reactions occur without substrate binding to the ruthenium center, but instead with precursor complex formation by hydrogen bonding. The free energies of the reactions vary over more than 90 kcal mol−1, but the rates are more dependent on the type of X−H bond involved than the associated ΔG°. There is a kinetic preference for substrates that have the transferring hydrogen atoms in close proximity, such as ortho‐tetrachlorobenzoquinone over its para‐isomer and 1,3‐cyclohexadiene over its 1,4‐isomer, perhaps hinting at the potential for concerted 2 e−/2 H+ transfers. |
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