A synthetic cycle for aryl C-F substitution comprising oxidative addition, ligand metathesis, and reductive elimination at a Cs-symmetric phosphorus triamide (1, P{N[o-NMe-C6H4]2}) is reported. Reaction of 1 with perfluoroarenes (ArF-F) results in C-F oxidative addition yielding fluorophosphoranes 1•[F][ArF]. The P-fluoro substituent is exchanged for hydride by treatment with DIBAL-H, generating hydridophosphoranes 1•[H][ArF]. Heating of 1•[H][ArF] regenerates 1 by C-H reductive elimination of ArF-H, where experimental and computational studies establish a concerted but highly asynchronous mechanism. The results provide well-characterized examples of the full triad of elementary mechanistic aryl C-X substitution steps at a single main group site.

中文翻译：

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PIII/PV 合成循环中的往返氧化加成、配体复分解和还原消除

报道了芳基 CF 取代的合成循环，包括在 Cs 对称磷三酰胺 (1, P{N[o-NMe-C6H4]2}) 上的氧化加成、配体复分解和还原消除。1 与全氟芳烃 (ArF-F) 的反应导致 CF 氧化加成，生成氟正膦 1•[F][ArF]。通过用 DIBAL-H 处理，P-氟取代基被交换为氢化物，生成氢化正膦 1•[H][ArF]。1•[H][ArF] 的加热通过 ArF-H 的 CH 还原消除再生 1，其中实验和计算研究建立了协调但高度异步的机制。结果提供了在单个主要基团位点处的基本机械芳基 CX 取代步骤的完整三元组的充分表征的例子。