第一长周期过渡金属羰基化合物脱硫机理的理论研究

This application is intended to quantum chemistry and quantum dynamics methods to explore the reaction mechanism of the interaction of the first long period transition metal carbonyl compounds with thiols. First, Theoretical calculated which experiments have studied the desulfurization reaction of transition metal carbonyl compounds, compared with the calculated results and experimental results, optimize screening a set of time-saving computing solutions. Secondly, based on the optimal computing solutions, study first long period transition metal carbonyl compounds with thiols between all possible reaction channels of reactants, intermediates, transition states and products were optimized, and by frequency analysis and intrinsic reaction coordinate (IRC) to confirm the intermediates and transition states. Which take advantage of the natural bonds orbital analysis method (NBO) to focus discussion study material of the chemical bonds and the sulfur atom of coordination, and to predict its desulfurization nature, theory clues can be provided to synthesized and developed with efficient desulfurization characteristics of transition metal carbonyl compounds. Finally, the project team combined experimental study on synthetic and desulfurization auxiliary experimental study of the theoretical calculations are screened out of transition metal carbonyl compounds, and other transition metal carbonyl compounds carried out comparing to verify the reliability of the theoretical research, the project can be to provide theoretical guidance and methods for experimental synthesis and application development.

本申请拟用量子化学、量子动力学方法来探索第一长周期过渡金属羰基化合物与硫醇相互作用的反应机理。首先理论计算实验已经研究的过渡金属羰基化合物脱硫反应，将计算结果和实验结果相比较，优化筛选出一套省时有效的计算方案。其次，依据最优计算方案，研究第一长周期过渡金属羰基化合物与硫醇之间所有可能的反应通道，对反应物、中间体、过渡态及产物进行优化，通过频率分析和内禀反应坐标(IRC)确认中间体和过渡态。其中利用自然键轨道分析法(NBO)，着重讨论研究物的化学键和硫原子的配位方式，来预测其脱硫性质，为能合成和开发出具有高效脱硫特性的过渡金属羰基化合物提供理论线索。最后，项目组结合实验研究，对理论计算所筛选出的过渡金属羰基化合物进行合成和脱硫方面的辅助实验研究，并与其他过渡金属羰基化合物进行比较，来验证理论研究的可靠性，项目可为实验合成和应用开发提供理论指导及方法。

含硫气体中羰基硫（COS）是目前公认的大气圈中重要的难降解污染物。本研究应用了密度泛函理论和实验手段，首次确定了COS催化水解反应过程中催化剂失活诱因，并借助实验手段对COS催化水解反应进行了实验验证，优化了类水滑石结构为前驱体的复合金属氧化物在催化水解COS反应中的实验条件。从理论计算和实验反应两方面都详细研究了COS的催化水解过程，提出了原创性的机理解释。因此，本课题有着重要的科学和现实意义。