Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany).
Angew Chem Int Ed Engl. 2014 Nov 24;53(48):13273-7. doi: 10.1002/anie.201408346. Epub 2014 Sep 24.
The trinuclear cationic zinc hydride cluster (IMes)3Zn3H4(THF)2 (1) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH2]2 with a Brønsted acid or by addition of the putative zinc dication (IMes)Zn(THF). A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhS-SPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)3SiH, giving silylformate as the main product.
三核阳离子锌氢簇[(IMes)3Zn3H4(THF)] (BPh4)2（1）可以通过质子化中性二氢锌[(IMes)ZnH2]2与布朗斯台德酸或添加假定的锌二阳离子[(IMes)Zn(THF)] (2+)获得。当用 PhS-SPh 氧化 1 时，形成了三桥连的噻吩醇络合物 2。1 通过甲醇或水的质子解得到相应的三核二价衍生物。在环境温度下，1 催化醛、酮和腈的硅氢化反应。当使用 (EtO)3SiH 时，在强制条件下也可以硅氢化二氧化碳，主要产物为硅基甲酸酯。
