Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0),ACS Catalysis

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Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-08-21 , DOI: 10.1021/acscatal.0c02514
Megan E Greaves _{1,

2} , Thomas O Ronson ₂ , Guy C Lloyd-Jones ₃ , Feliu Maseras ₄ , Stephen Sproules ₅ , David J Nelson ₁

Affiliation

The mechanism of the reactions between dppf-Ni⁰ complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ²-dppf)(κ¹-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand.

中文翻译：

意想不到的镍络合物形态开启了烷基卤化物与 dppf-Nickel(0) 反应的替代途径

通过动力学和机理实验以及DFT计算研究了dppf-Ni ⁰配合物与卤代烷之间的反应机理。活性物质是[Ni(κ ² -dppf)(κ ¹ -dppf)]，它与烷基卤发生卤化物夺取反应，并快速捕获形成的烷基自由基。通过添加游离 dppf 配体，[Ni(COD)(dppf)] 与卤代烷的反应速率以及原型镍催化的卤代烷 Kumada 交叉偶联反应的产率显着提高。

更新日期：2020-09-20

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