College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Molecules. 2020 Dec 24;26(1):50. doi: 10.3390/molecules26010050.
Unlike the usual method of CO ( = 1, 2) hydrogenation using H directly, HS and HSiSH (silicon-activated HS) were selected as alternative hydrogen sources in this study for the CO hydrogenation reactions. Our results suggest that it is kinetically infeasible for hydrogen in the form of HS to transfer to CO at low temperatures. However, when HSiSH is employed instead, the title reaction can be achieved. For this approach, the activation of CO is initiated by its interaction with the HSiSH molecule, a reactive species with both a hydridic H and protonic H. These active hydrogens are responsible for the successive C-end and O-end activations of CO and hence the final product (HCOOH). This finding represents a good example of an indirect hydrogen source used in CO hydrogenation through reactivity tuned by silicon incorporation, and thus the underlying mechanism will be valuable for the design of similar reactions.
与通常使用 H 直接进行 CO(=1,2)加氢的方法不同，在本研究中选择 HS 和 HSiSH（硅活化 HS）作为 CO 加氢反应的替代氢源。我们的结果表明，在低温下，HS 形式的氢向 CO 转移在动力学上是不可行的。然而，当使用 HSiSH 时，则可以实现该标题反应。对于这种方法，CO 的活化是通过其与 HSiSH 分子的相互作用引发的，HSiSH 分子是一种具有氢化物 H 和质子 H 的反应性物质。这些活性氢负责 CO 的连续 C 端和 O 端的活化，从而生成最终产物（HCOOH）。这一发现代表了通过硅掺入调谐反应性在 CO 加氢中使用间接氢源的一个很好的例子，因此，该潜在机制对于类似反应的设计将具有重要价值。
