Convenient Access to Gallium(I) Cations through Hydrogen Elimination from Cationic Gallium(III) Hydrides
Convenient Access to Gallium(I) Cations through Hydrogen Elimination from Cationic Gallium(III) Hydrides
复制标题
通过从阳离子镓（III）氢化物中消除氢，方便地获得镓（I）阳离子
DOI：
10.1021/acs.inorgchem.9b02136
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发表时间：
2019
影响因子：
4.6
通讯作者：
Powell, Douglas R.
中科院分区：
文献类型：
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作者：
Wehmschulte, Rudolf J.;Peverati, Roberto;Powell, Douglas R.
虽然镓化合物XnGaH 3-n（X=单阴离子取代基）通常是稳定的化合物，但阳离子芳烃溶剂化物种[H2 Ga（arene）2]+在室温下自发消除氢，得到芳烃溶剂化镓（I）化合物[Ga（PhF）2][CHB 11 Cl 11]（1）和[Ga（Ph 3CH）][B（C6 F5）4]（3）。一个关键的要求似乎是弱配位阴离子的存在。使用碱性更强的三氟甲磺酰亚胺阴离子[NTf 2]−会逆转稳定性，即，氢化镓（III）H2 GaNTf 2（4）比镓（I）化合物GaNTf 2（5）更稳定。实验结果得到了DFT计算的支持。化合物1和3可作为催化剂用于2，4，4-三甲基-1-戊烯的齐聚反应和二苯甲酮与1-己烯的硅氢加成反应。
Although gallium hydridesXnGaH3–n(X= monoanionic substituent) are usually stable compounds, cationic arene-solvated species [H2Ga(arene)2]+spontaneously eliminate dihydrogen at room temperature to afford the arene-solvated gallium(I) compounds [Ga(PhF)2][CHB11Cl11] (1) and [Ga(Ph3CH)][B(C6F5)4] (3). A key requirement appears to be the presence of a weakly coordinating anion. Use of the more basic triflimide anion, [NTf2]−, reverses the stability, i.e., the gallium(III) hydride H2GaNTf2(4) is more stable than the gallium(I) compound GaNTf2(5). The experimental results are supported by DFT calculations. Compounds1and3can be used as catalysts for the oligomerization of 2,4,4-trimethyl-1-pentene and the hydrosilylation of benzophenone and 1-hexene.