Department of Chemistry, University of California, Riverside, California, CA 92521, USA.
Molecules. 2020 Jul 7;25(13):3090. doi: 10.3390/molecules25133090.
Although molybdenum sulfide materials show promise as electrocatalysts for proton reduction, the hydrido species proposed as intermediates remain poorly characterized. We report herein the synthesis, reactions and spectroscopic properties of a molybdenum-hydride complex featuring an asymmetric MoS core. This molecule displays rich redox chemistry with electrochemical couples at = -0.45, -0.78 and -1.99 V vs. Fc/Fc. The corresponding hydrido-complexes for all three redox levels were isolated and characterized crystallographically. Through an analysis of solid-state bond metrics and DFT calculations, we show that the electron-transfer processes for the two more positive couples are centered predominantly on the pyridinediimine supporting ligand, whereas for the most negative couple electron-transfer is mostly Mo-localized.
尽管硫化钼材料作为质子还原的电催化剂具有很大的潜力，但作为中间体的氢化物物种的特性仍未得到很好的描述。我们在此报告了一种具有不对称 MoS 核的钼-氢化物配合物的合成、反应和光谱性质。该分子具有丰富的氧化还原化学性质，电化学对在 Fc/Fc 相对于 = -0.45、-0.78 和 -1.99 V 处。所有三个氧化还原水平的相应氢化物配合物均通过电化学方法分离和结晶学方法进行了表征。通过对固态键参数和 DFT 计算的分析，我们表明，两个更正的对的电子转移过程主要集中在吡啶二亚胺支撑配体上，而对于最负的对，电子转移主要是 Mo 局部化的。
