Gupta Ankur K, Topolski Josey E, Nickson Kathleen A, Jarrold Caroline Chick, Raghavachari Krishnan
Department of Chemistry , Indiana University 800 E. Kirkwood Avenue , Bloomington , Indiana 47405 , United States.
J Phys Chem A. 2019 Aug 22;123(33):7261-7269. doi: 10.1021/acs.jpca.9b04079. Epub 2019 Aug 12.
A combined experimental and computational study of H reactions with small MoS clusters ranging from subsulfide ( ∼ ) to hypersulfide ( > 2) is presented. Results suggest that the subsulfides react with H primarily by insertion of a more reduced Mo center into the H-H bond, forming a dihydride product. We find that this reaction occurs up to Mo oxidation states of +4. For the subsulfides containing a second metal in a sufficiently low oxidation state, a second insertion of H occurs, leading to a tetrahydride product. The reaction mechanisms of the sulfides are found to be very similar, albeit slightly higher energetically to those of the analogous oxosulfides that are also observed at low abundances in the experiments. In addition, the experimental results show an overall reduction of hypersulfides in the presence of H, suggesting loss of HS neutral molecules.
本文介绍了对H与从亚硫化物（~）到超硫化物（>2）的小MoS团簇反应的实验与计算相结合的研究。结果表明，亚硫化物与H主要通过将一个还原程度更高的Mo中心插入H-H键来反应，形成二氢化物产物。我们发现，这种反应在Mo氧化态达到+4时都会发生。对于含有处于足够低氧化态的第二种金属的亚硫化物，会发生第二次H插入，生成四氢化物产物。发现硫化物的反应机制非常相似，尽管在能量上比在实验中低丰度下也观察到的类似氧硫化物略高。此外，实验结果表明，在有H存在的情况下，超硫化物总体上会减少，表明HS中性分子会损失。
