C-H Bond Trifluoromethylation of Arenes Enabled by a Robust, High-Valent Nickel(IV) Complex
C-H Bond Trifluoromethylation of Arenes Enabled by a Robust, High-Valent Nickel(IV) Complex
复制标题
DOI：
10.1002/anie.201706237
复制
发表时间：
2017-10-09
影响因子：
16.6
通讯作者：
Nebra, Noel
中科院分区：
文献类型：
--
作者：
D'Accriscio, Florian;Borja, Pilar;Nebra, Noel
合成了稳定的高价Ni-IV配合物[（Py）（2）（NiF 2）-F-IV（CF 3）（2）]（Py=吡啶），并通过NMR光谱、X射线衍射和元素分析对其进行了充分表征。它与芳香族化合物在25 ℃下反应，以几乎定量的产率形成相应的三氟甲苯。单体和二聚体（NiCF 3）-C-III配合物2 Py和2被确定为关键中间体，并且通过EPR光谱和X射线衍射明确地确定了它们的结构。初步动力学研究结合反应中间体的分离证实，C-H键断裂/C-CF 3键形成序列可以发生在（NiCF 3）-C-IV和（NiCF 3）-C-III中心。
The robust, high-valent Ni-IV complex [(Py)(2)(NiF2)-F-IV(CF3)(2)] (Py=pyridine) was synthesized and fully characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. It reacts with aromatic compounds at 25 degrees C to form the corresponding benzotrifluorides in nearly quantitative yield. The monomeric and dimeric (NiCF3)-C-III complexes 2Py and 2 were identified as key intermediates, and their structures were unambiguously determined by EPR spectroscopy and X-ray diffraction. Preliminary kinetic studies in combination with the isolation of reaction intermediates confirmed that the C-H bond-breaking/C-CF3 bond-forming sequence can occur both at (NiCF3)-C-IV and (NiCF3)-C-III centers.