A Carbon-Bridged Digallium Compound as a Chelating Lewis Acid: Complexation of Thiophenolate and Benzoate Anions by H5C6−CH2−C(SiMe3)[Ga(CH2tBu)2]2
A Carbon-Bridged Digallium Compound as a Chelating Lewis Acid: Complexation of Thiophenolate and Benzoate Anions by H5C6−CH2−C(SiMe3)[Ga(CH2tBu)2]2
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作为螯合路易斯酸的碳桥二镓化合物：H5C6−CH2−C(SiMe3)[Ga(CH2tBu)2]2 络合硫代酚酸根和苯甲酸根阴离子
DOI：
10.1021/om800068s
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发表时间：
2008
期刊：
影响因子：
2.8
通讯作者：
A. Hepp
中科院分区：
文献类型：
--
作者：
W. Uhl;M. Claesener;A. Hepp
二镓化合物 H5C6−CH2C(SiMe3)(GaCl2)2 (6) 可以通过苯基（三甲基甲硅烷基）乙炔与 H−GaCl2 的 2 倍加氢反应轻松获得。用新戊基锂处理，通过取代所有四个氯原子得到相应的四新戊基化合物7。化合物 7 有两个配位不饱和镓原子连接到一个碳原子上，因此适合用作螯合路易斯酸。因此，溶解在1,2-二氟苯中的四丁基苯硫酚铵很容易与7反应得到加合物8，其中苯硫酚基团的硫原子与两个镓原子配位形成四元CGa2S杂环。用苯甲酸根阴离子处理7形成类似的化合物(9)。与 8 相比，结构基序略有不同，因为苯甲酸酯配体的每个氧原子与一个镓原子配位，形成六元 Ga2C2O2 杂环。
The digallium compound H5C6−CH2C(SiMe3)(GaCl2)2 (6) is easily available by the 2-fold hydrogallation of phenyl(trimethylsilyl)ethyne with H−GaCl2. Its treatment with neopentyllithium gave the corresponding tetraneopentyl compound 7 by the replacement of all four chlorine atoms. Compound 7 has two coordinatively unsaturated gallium atoms attached to one carbon atom and, hence, is suitable to act as a chelating Lewis acid. Accordingly, tetrabutylammonium thiophenolate dissolved in 1,2-difluorobenzene reacted readily with 7 to afford the adduct 8, in which the sulfur atom of the thiophenolato group is coordinated by both gallium atoms to form a four-membered CGa2S heterocycle. A similar compound (9) was formed upon treatment of 7 with the benzoate anion. A slightly different structural motif compared to 8 resulted because each oxygen atom of the benzoate ligand is coordinated to one gallium atom to give a six-membered Ga2C2O2 heterocycle.