Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, Co^III(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (Co^III(qpy)OOR + R′H → Co^II(qpy) + R′^• + ROOH). The resulting alkyl radical (R′^•) reacts rapidly with O₂ to form alkylperoxy radical (R′OO^•), which is efficiently scavenged by Co^II(qpy) to give Co^III(qpy)OOR′ (Co^II(qpy) + R′OO^• → Co^III(qpy)OOR′). This unique reactivity enables Co^III(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O₂ → R′OOH) under 1 atm air and at room temperature.

中文翻译：

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钴 (III) 烷基过氧配合物催化有机底物的室温有氧过氧化

烃类的室温有氧氧化是非常理想的，并且仍然是一个巨大的挑战。在这里，我们报告了一系列高度亲电的钴 (III) 烷基过氧配合物，Co ^III (qpy)OOR 由平面四齿四联吡啶配体支持，该配体可以在环境条件下直接从烃 (R'H) 中提取 H 原子 (Co ^III (qpy) OOR + R'H → Co ^II (qpy) + R' ^• + ROOH)。得到的烷基 (R' ^• ) 与 O ₂迅速反应形成烷基过氧自由基 (R'OO ^• )，后者被 Co ^II (qpy)有效清除，得到 Co ^III (qpy)OOR' (Co ^II (qpy) + R'OO ^•→ Co ^III (qpy)OOR')。这种独特的反应性使 Co ^III (qpy)OOR在 1 个大气压的空气和室温下成为碳氢化合物（R'H + O ₂ → R'OOH）有氧过氧化的有效催化剂。