Cheng Yukun, Huh Daniel N, Tonks Ian A
Department of Chemistry and Chemical Biology, Cornell University, 365 Spencer T. Olin Research Wing, Ithaca, New York, USA.
Department of Chemistry, University of Rhode Island, Kingston, Rhode Island, USA.
Dalton Trans. 2024 Jun 4;53(22):9510-9515. doi: 10.1039/d4dt01412j.
Metal-mediated inner-sphere N-N coupling is an uncommon route to N-N bond formation. Herein, we report a mechanistic study of pyrazole formation oxidation-induced N-N coupling of diazatitanacycles. In TEMPO oxidation reactions, the first of two oxidations is rate limiting and TEMPO coordination to Ti is critical for reactivity. In oxidations with Fc salts, coordinating counteranions such ( Cl) aid an "inner-sphere-like" oxidation.
金属介导的内球N-N偶联是形成N-N键的一种不常见途径。在此，我们报道了吡唑形成——重氮钛杂环的氧化诱导N-N偶联的机理研究。在TEMPO氧化反应中，两次氧化中的第一次是限速步骤，且TEMPO与Ti的配位对反应活性至关重要。在用Fc盐进行的氧化反应中，配位抗衡阴离子（如Cl）有助于“类内球”氧化。
