Homogeneous catalysis and biocatalysis have been widely applied in synthetic, medicinal, and energy chemistry as well as synthetic biology. Driven by developments of new computational chemistry methods and better computer hardware, computational chemistry has become an essentially indispensable mechanistic “instrument” to help understand structures and decipher reaction mechanisms in catalysis. In addition, synergy between computational and experimental chemistry deepens our mechanistic understanding, which further promotes the rational design of new catalysts. In this Account, we summarize new or deeper mechanistic insights (including isotope, dispersion, and dynamical effects) into several complex homogeneous reactions from our systematic computational studies along with subsequent experimental studies by different groups. Apart from uncovering new mechanisms in some reactions, a few computational predictions (such as excited-state heavy-atom tunneling, steric-controlled enantioswitching, and a new geminal addition mechanism) based on our mechanistic insights were further verified by ensuing experiments.

均相催化和生物催化已广泛应用于合成、药物和能源化学以及合成生物学。在新的计算化学方法和更好的计算机硬件发展的推动下，计算化学已成为帮助理解催化结构和破译反应机制的必不可少的机械“工具”。此外，计算化学和实验化学之间的协同作用加深了我们对机理的理解，进一步促进了新催化剂的合理设计。在这个帐户中，我们从我们的系统计算研究以及不同小组的后续实验研究中，将新的或更深层次的机理见解（包括同位素、色散和动力学效应）总结为几个复杂的均相反应。