The heme paradigm where Fe=O acts as the C–H oxidant and Fe–OH rebounds with the formed carbon‐centered radical guides the design of the prototypical synthetic hydroxylation catalyst. We are exploring methods to evolve beyond the metal‐oxo oxidant and hydroxide rebound, to incorporate a wider array of functional group. We have demonstrated the application of CoII(OTf)2 (10 mol% catalyst; OTf = trimfluoromethanesulfonate) in combination with polydentate N‐donor ligands (e.g. BPMEN = N,N′‐dimethyl‐N,N′‐bis(pyrid‐2‐ylmethyl)ethane‐1,2‐diamine) and Selectfluor in the oxidative fluorination of saturated hydrocarbons in high yields. The addition of CsF to the reaction mixture induced near‐quantitative yields of fluorinated saturated hydrocarbons (>90% yield of fluorinated product). For 1‐hydroxy, 1‐acetyl, 1‐carboxy‐, and 1‐acetamido‐adamantane, we demonstrated fluorination at the 3‐position. We propose two mechanisms for the CoII‐catalyzed reaction: either (i) an N‐radical, derived from Selectfluor, acted as the C–H oxidant followed by radical rebound with CoIII–F; or (ii) a CoIV–(F)2 species was the C–H oxidant followed by radical rebound with CoIII–F. Our combined spectroscopic, kinetic, and chemical trapping evidence suggested that an N‐radical was not the active oxidant. We concluded that a CoIV–(F)2 species was the likely active oxidant and CoIII–F was the likely F‐atom donor to a carbon centered radical producing a C–F bond.

中文翻译：

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饱和烃氧化氟化物中的高价二氟化钴


Fe=O 充当 C-H 氧化剂，Fe-OH 与形成的碳心自由基一起反弹的血红素范式指导了原型合成羟基化催化剂的设计。我们正在探索超越金属氧化剂和氢氧化物反弹的方法，以纳入更广泛的官能团。我们已经展示了 CoII（OTf）2（10 mol% 催化剂;OTf = 三氟甲磺酸盐）与多齿 N-供体配体（例如 BPMEN = N，N′-二甲基-N，N′-双（吡啶-2-基甲基）乙烷-1,2-二胺）和 Selectfluor 在饱和烃的氧化氟化中以高产率进行。向反应混合物中添加 CsF 诱导了氟化饱和烃的近定量产率（氟化产物的 >90% 产率）。对于 1-羟基、1-乙酰基、1-羧基-和 1-乙酰氨基-金刚烷，我们证明了 3-位置的氟化。我们提出了 CoII 催化反应的两种机制：要么 （i） 来自 Selectfluor 的 N-自由基充当 C-H 氧化剂，然后自由基与 CoIII-F 反弹;或 （ii） CoIV-（F）2 物质是 C-H 氧化剂，然后是 CoIII-F 的自由基反弹。我们结合光谱、动力学和化学捕获证据表明，N-自由基不是活性氧化剂。我们得出结论，CoIV-（F）2 物质可能是活性氧化剂，而 CoIII-F 可能是产生 C-F 键的碳中心自由基的 F 原子供体。