Solid-state radical generation is an attractive but underutilized methodology in the catalytic strong bond activation process, such as the aryl-halide bond. Traditionally, such a process of strong bond activation relied upon the use of transition metal complexes or strongly reducing photocatalysts in organic solvents. The generation of the aryl radical from aryl halides in the absence of transition-metal or external stimuli, such as light or cathodic current, remains an elusive process. In this study, we describe a reduced organic hydrocarbon, which can act as a super reductant in the solid state to activate strong bonds by solid-state single electron transfer (SSSET) under the influence of mechanical energy leading to a catalytic strategy based on the mechano-SSSET or mechanoredox process. Here, we investigate the solid-state synthesis of the super electron donor phenalenyl anion in a ball mill and its application as an active catalyst in strong bond (aryl halide) activation. Aryl radicals generated from aryl halides by employing this strategy are competent for various carbon–carbon bond-forming reactions under solvent-free and transition metal-free conditions. We illustrate this approach for partially soluble or insoluble polyaromatic arenes in accomplishing solid–solid C–C cross-coupling catalysis, which is otherwise difficult to achieve by traditional methods using solvents.

中文翻译：

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用于催化芳基卤化物键活化的还原有机烃的机械化学固态单电子转移

固态自由基生成是催化强键活化过程（例如芳基卤化物键）中一种有吸引力但未充分利用的方法。传统上，这种强键活化过程依赖于使用过渡金属络合物或有机溶剂中的强还原光催化剂。在没有过渡金属或外部刺激（例如光或阴极电流）的情况下，芳基卤化物生成芳基仍然是一个难以捉摸的过程。在这项研究中，我们描述了一种还原的有机碳氢化合物，它可以作为固态的超级还原剂，在机械能的影响下通过固态单电子转移 (SSSET) 激活强键，从而导致基于机械-SSSET 或机械氧化还原过程。这里，我们研究了超电子供体苯二甲酸阴离子在球磨机中的固态合成及其在强键（芳基卤化物）活化中作为活性催化剂的应用。通过采用这种策略由芳基卤化物产生的芳基自由基能够在无溶剂和无过渡金属的条件下进行各种碳-碳键形成反应。我们举例说明了这种用于部分可溶性或不溶性聚芳烃的方法，以实现固-固 C-C 交叉偶联催化，否则使用溶剂的传统方法很难实现。通过采用这种策略由芳基卤化物产生的芳基自由基能够在无溶剂和无过渡金属的条件下进行各种碳-碳键形成反应。我们举例说明了这种用于部分可溶性或不溶性聚芳烃的方法，以实现固-固 C-C 交叉偶联催化，否则使用溶剂的传统方法很难实现。通过采用这种策略由芳基卤化物产生的芳基自由基能够在无溶剂和无过渡金属的条件下进行各种碳-碳键形成反应。我们举例说明了这种用于部分可溶性或不溶性聚芳烃的方法，以实现固-固 C-C 交叉偶联催化，否则使用溶剂的传统方法很难实现。