Air-Stable Tetrazene Radical Cation Salts: Structural Requirements and Oxidation Catalysts

空气稳定的四嗪自由基阳离子盐:结构要求和氧化催化剂

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Abstract

In this study, stable tetrazene radical cation salts were synthesized and characterized for the first time. The radical cation derived from 1,2-di(2-azaadamantan-2-yl)diazene (DAD) was isolated as an air-stable solid, retaining its integrity for at least 120 days at ambient temperature (∼25 °C) and pressure. X-ray crystallography and electron spin-resonance spectroscopy revealed the delocalization of the unpaired electron over the tetrazene core and into the adamantane framework. DAD undergoes two well-separated, reversible redox processes and displays high catalytic activity for alcohol oxidation under mild conditions. Systematic structural modifications identified the key framework features governing the radical cation stability and catalytic performance.

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