Cleavage of C(sp3)–F Bonds in Trifluoromethylarenes Using a Bis(NHC)nickel(0) Complex,Journal of the American Chemical Society

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Cleavage of C(sp3)–F Bonds in Trifluoromethylarenes Using a Bis(NHC)nickel(0) Complex
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-10-28 , DOI: 10.1021/jacs.0c09639
Hiroaki Iwamoto ₁ , Hiroto Imiya ₁ , Masato Ohashi ₂ , Sensuke Ogoshi ₁

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The first example of the oxidative addition of a C(sp3)-F bond in trifluoromethylarenes to a nickel(0) complex is described. A nickel(0) complex that bears two N-heterocyclic carbene (NHC) ligands of low steric demand is able to cleave C(sp3)-F bonds of trifluoromethylarenes to afford the corresponding trans-difluorobenzyl nickel(II) fluoride complexes. Isolation and characterization studies suggested that the cleavage of the C(sp3)-F bond proceeds via an η2-arene nickel(0) complex. Taking advantage of the reactivity of these nickel(II) fluoride complexes, we developed a catalytic hydrodefluorination of trifluoromethylarenes using hydrosilanes. A computational study indicated that the electron-rich nickel(0) center supported by two relatively small NHC ligands cleaves the C(sp3)-F bond via a syn-SN2' mechanism.

中文翻译：

使用双 (NHC) 镍 (0) 配合物裂解三氟甲基芳烃中的 C(sp3)–F 键

描述了将三氟甲基芳烃中的 C(sp3)-F 键氧化加成到镍 (0) 配合物的第一个例子。带有两个低空间位阻要求的 N-杂环卡宾 (NHC) 配体的镍 (0) 配合物能够裂解三氟甲基芳烃的 C(sp3)-F 键，得到相应的反式二氟苄基镍 (II) 氟化物配合物。分离和表征研究表明，C(sp3)-F 键的裂解是通过 η2-芳烃镍 (0) 配合物进行的。利用这些氟化镍 (II) 配合物的反应性，我们开发了一种使用氢硅烷对三氟甲基芳烃进行催化加氢脱氟的方法。一项计算研究表明，由两个相对较小的 NHC 配体支持的富电子镍 (0) 中心通过 syn-SN2' 机制裂解 C(sp3)-F 键。

更新日期：2020-10-28

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