Connecting Organometallic Ni(III) and Ni(IV): Reactions of Carbon-Centered Radicals with High-Valent Organonickel Complexes
| Autor: | James R. Bour, Devin M. Ferguson, Melanie S. Sanford, Edward J. McClain, Jeff W. Kampf |
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| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Radical Aryl chemistry.chemical_element General Chemistry 010402 general chemistry Carbon centered radicals 01 natural sciences Biochemistry Redox Catalysis 0104 chemical sciences Nickel chemistry.chemical_compound Colloid and Surface Chemistry chemistry Polymer chemistry Reactivity (chemistry) Alkyl |
| Zdroj: | Journal of the American Chemical Society. 141:8914-8920 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | This paper describes the one-electron interconversions of isolable NiIII and NiIV complexes through their reactions with carbon-centered radicals (R•). First, model NiIII complexes are shown to react with alkyl and aryl radicals to afford NiIV products. Preliminary mechanistic studies implicate a pathway involving direct addition of a carbon-centered radical to the NiIII center. This is directly analogous to the known reactivity of NiII complexes with R•, a step that is commonly implicated in catalysis. Second, a NiIV-CH3 complex is shown to react with aryl and alkyl radicals to afford C-C bonds via a proposed SH2-type mechanism. This pathway is leveraged to enable challenging H3C-CF3 bond formation under mild conditions. Overall, these investigations suggest that NiII/III/IV sequences may be viable redox pathways in high-oxidation-state nickel catalysis. |
| Databáze: | OpenAIRE |
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