Mechanochemistry of Cationic Cobaltocenium Mechanophore
Mechanochemistry of Cationic Cobaltocenium Mechanophore
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DOI：
10.1021/jacs.1c05233
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发表时间：
2021-07-20
影响因子：
15
通讯作者：
Tang, Chuanbing
中科院分区：
文献类型：
--
作者：
Cha, Yujin;Zhu, Tianyu;Tang, Chuanbing
最近对茂金属机械团的机械化学研究揭示了这些热稳定性和化学稳定性的有机金属化合物的力响应性。在这项工作中，我们报告了主链含钴-镍聚合物机械化学的实验和计算研究的结合。阳离子钴镉的酯衍生物虽然与中性二茂铁等电子，但在它们的二茂铁类似物所适应的非机械控制实验条件下不稳定。用提供电子的c -烷基取代吸电子的c -酯键，获得了必要的稳定性，并使钴镉的机械化学性质得以评估。尽管它们具有很高的键解离能，但在声机械激活下，钴镉机械载体是主链断裂的选择性位点。计算CoGEF计算表明，钴铈的反离子的存在通过促进离解的剥离机制以及初始滑移起着至关重要的作用。
Recent research on the mechanochemistry of metallocene mechanophores has shed light on the force-responsiveness of these thermally and chemically stable organometallic compounds. In this work, we report a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltoce-nium- containing polymers. Ester derivatives of the cationic cobaltocenium, though isoelectronic to neutral ferrocene, are unstable in the nonmechanical control experimental conditions that were accommodated by their ferrocene analogs. Replacing the electron withdrawing C-ester linkages with electron-donating C-alkyls conferred the necessary stability and enabled the mechanochemistry of the cobaltocenium to be assessed. Despite their high bond dissociation energy, cobaltocenium mechanophores are found to be selective sites of main chain scission under sonomechanical activation. Computational CoGEF calculations suggest that the presence of a counterion to cobaltocenium plays a vital role by promoting a peeling mechanism of dissociation in conjunction with the initial slipping.