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.
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| http://dx.doi.org/10.1039/d4dt01412j | DOI Listing |
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