Models of dithiolate rhenium(V)–oxo and –thio complexes and Re^VII (Re^VIIO₂ and Re^VIIOS) intermediates are studied computationally using DFT(B3LYP). The analysis of the Re–E bond (E = O, S) shows that the two lone pairs (P_x, P_y) on the oxo and thio ligands are strongly polarized to the Re^V and Re^VII centers, forming partial π bonds, which agree with the bond‐order analysis of 2 (one σ + two partial π bonds). The lone pairs on the thio ligands are less polarized than on the oxo ligand. The Re^VO and Re^VS bond strengths are calculated to be approximately 163.7 ± 1.8 kcal mol^–1 and 123 ± 3 kcal mol^–1, respectively. The Re^VIIO and Re^VIIS bond strengths are calculated to be 118.7 ± 1.2 kcal mol^–1 and 80.5 ± 3.5 kcal mol^–1, respectively. The calculated oxo– and thio–rhenium bond strengths and the thermochemistry of the OAT (oxygen‐atom transfer) cycle support that Re^VIIO₂ and Re^VIIOS are the key intermediates in the OAT (oxygen atom transfer) and SAT (sulfur atom transfer) reactions.

中文翻译：

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chemistry（V）催化剂和R（VII）中间体中氧代和硫代配体的热化学和键性质：密度泛函计算

使用DFT（B3LYP）通过计算研究了_二硫代late（V）-氧代和-硫代配合物以及Re ^VII（Re ^VII O ₂和Re ^VII OS）中间体的模型。Re-E键（E = O，S）的分析表明，氧代和硫代配体上的两个孤对（P _x，P _y）强烈极化到Re ^V和Re ^VII中心，形成部分π键，它与2（一个σ+两个部分π键）的键序分析一致。硫代配体上的孤对极化比氧代配体上的孤对弱。Re ^V O和Re ^VS的结合强度经计算约为163.7±1.8 kcal mol^{分别为–1}和123±3 kcal mol ^–1。Re ^VII O和Re ^VII S的结合强度经计算分别为118.7±1.2 kcal mol ^–1和80.5±3.5 kcal mol ^–1。计算得出的氧-和硫-hen键强度以及OAT（氧原子转移）循环的热化学表明，Re ^VII O ₂和Re ^VII OS是OAT（氧原子转移）和SAT（硫原子）的关键中间体转移）反应。