In this work, we report the generation and characterization of two new Co(III)-peroxo complexes and . is best described as a mononuclear Co-(O) complex that exhibits an O-isotope sensitive OO bond stretching vibration at 845(−49) cm, indicating a relatively weak peroxo moiety compared to those of other Co-(O) complexes reported previously. Complex is a Co-peroxo-arylboronate species having a rare {CoOOBO} five-membered metallocycle, which is structurally characterized using X-ray crystallography. Investigations of the reaction mechanism using density functional theory calculations show that likely undergoes a nucleophilic attack to an arylboronic acid, which is generated by hydrolysis of the BPh anion in wet acetonitrile solution, to first form a Co-peroxo-arylboronic acid adduct, followed by the loss of one benzene molecule to generate the five-membered metallocycle. The entire reaction is thermodynamically favorable. Taken together, the conversion of to represents the discovery of a novel nucleophilic reactivity that can be carried out by mononuclear Co(III)-peroxo complexes.

中文翻译：

---

由 Co(III)-过氧物质的亲核反应形成的 Co(III)-过氧芳基硼酸盐络合物

在这项工作中，我们报告了两种新型 Co(III)-过氧配合物 和 的生成和表征。最好的描述是单核Co-(O)配合物，在845(−49) cm处表现出O-同位素敏感的OO键伸缩振动，表明与之前报道的其他Co-(O)配合物相比，其过氧部分相对较弱。配合物是一种 Co-peroxo-arylboronate 物质，具有稀有的 {CoOOBO} 五元金属环，使用 X 射线晶体学对其结构进行了表征。使用密度泛函理论计算对反应机理的研究表明，可能会经历对芳基硼酸的亲核攻击，芳基硼酸是由 BPh 阴离子在湿乙腈溶液中水解产生的，首先形成 Co-过氧-芳基硼酸加合物，然后形成失去一个苯分子以生成五元金属环。整个反应在热力学上是有利的。总而言之，to 的转化代表了一种新的亲核反应性的发现，该反应性可以通过单核 Co(III)-过氧配合物进行。