College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, P. R. China.
Key Laboratory of Carbon Materials of Zhejiang Province, Wenzhou University, Wenzhou, 325035, P. R. China.
Chemistry. 2023 Jun 13;29(33):e202300552. doi: 10.1002/chem.202300552. Epub 2023 Apr 27.
Inspired by alkene addition to the Ru and Re tris(thiolate) complexes via carbon-sulfur bond formation/cleavage reactions along with a periodic extension catalysis notion, a comparative study of the electronic structures, mechanisms, and reactivities for ethylene addition to the Os and Tc tris(thiolate) complexes was performed by DFT and high-level ab initio quantum calculations. The oxidized Os and Tc complexes were revealed to exhibit sufficient radical characters on the ligands to support their reaction with ethylene, whereas neutral Tc tris(thiolate) complex featuring little thiyl radical character renders no reactivity toward ethylene. Differential reactivities of these tris(thiolate) complexes was deemed to derive from the synergy of the thiyl radical character, the electronegativity, the row, and the charge. Extending from Ru and Re tris(thiolate) complexes to their Os and Tc counterparts can help us to get insightful rationales that would promote further research on alkene addition to metal-stabilized thiyl radicals.
受通过碳硫键形成/断裂反应将烯烃加成到 Ru 和 Re 三（硫醇）配合物以及周期性扩展催化概念的启发，通过 DFT 和高级从头算量子计算对 Os 和 Tc 三（硫醇）配合物中乙烯加成的电子结构、机理和反应性进行了比较研究。氧化的 Os 和 Tc 配合物被揭示出在配体上具有足够的自由基特性，以支持它们与乙烯的反应，而具有很少硫自由基特性的中性 Tc 三（硫醇）配合物对乙烯没有反应性。这些三（硫醇）配合物的不同反应性被认为源自硫自由基特性、电负性、行和电荷的协同作用。将 Ru 和 Re 三（硫醇）配合物扩展到它们的 Os 和 Tc 对应物可以帮助我们获得有洞察力的基本原理，从而促进对金属稳定硫自由基的烯烃加成的进一步研究。
