C-H and C-N Bond Activation of Tertiary Amines by Cationic Germanium(IV) Corrole
C-H and C-N Bond Activation of Tertiary Amines by Cationic Germanium(IV) Corrole
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DOI：
10.1021/acs.organomet.9b00237
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发表时间：
2019-06-24
期刊：
影响因子：
2.8
通讯作者：
Fang, Huayi
中科院分区：
文献类型：
--
作者：
Jing, Huize;Ge, Haonan;Fang, Huayi
叔胺中的C-H键和C-N键在室温下被Ge(IV)Corole阳离子[(TPFC)Ge](+)激活。观察到C-H键的断裂，它对叔胺中的β和伽马位置具有独特的选择性，而过渡金属化合物促进的C-H键断裂中的α位置选择性是众所周知的。用密度泛函理论(DFT)计算的初步机理研究表明，C-N键的活化可能通过亲核取代途径进行。虽然现阶段C-H键的活化机理尚不清楚，但也计算了Lewis酸碱协同反应路径。
C-H and C-N bonds in tertiary amines were activated by the germanium(IV) corrole cation [(TPFC)Ge](+) (TPFC = 5,10,15-tris(pentafluorophenyl) corrole) at room temperature. Cleavage of C-H bonds with a unique selectivity for the beta- and gamma-positions in tertiary amines was observed, in contrary to the well-studied alpha-position selectivity in C-H bond cleavage promoted by transition-metal compounds. Preliminary mechanism studies using density functional theory (DFT) calculation indicated a nucleophilic substitution pathway for C-N bond activation. Although the mechanism for the C-H bond activation was not clear at the present stage, a cooperative Lewis acid/base reaction pathway was also calculated.