Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals
Carboxylate as a Non-innocent L-Ligand: Computational and Experimental Search for Metal-Bound Carboxylate Radicals
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DOI：
10.1021/acs.orglett.2c01356
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发表时间：
2022-06-03
期刊：
影响因子：
5.2
通讯作者：
V. Alabugin, Igor
中科院分区：
文献类型：
--
作者：
Kuhn, Leah;Vil, Vera A.;V. Alabugin, Igor
我们表明，羧酸根作为一个L-配体与某些高自旋过渡金属中心。这种配位保留了通过氢原子转移进行C-H活化所需的O-自由基特征。新的C-自由基被金属捕获，随后还原消除，导致正式的C-H酰氧基化。通过螺环丙基部分引入的杂交效应，使RCO 2自由基的脱羧作用最小化。
We show that the carboxylate radical acts as an L-ligand with certain high-spin transition metal centers. Such coordination preserves the O-radical character needed for C-H activation via hydrogen atom transfer. Capture of the new C-radical by the metal and subsequent reductive elimination leads to formal C-H acyloxylation. Decarboxylation of the RCO2 radical is minimized through hybridization effects introduced by spiro-cyclopropyl moiety.