Although silane diamine copolymers have captured the attention of the catalysis community, the optimization of their synthesis and end uses have yet to be explored. In this study, a well-defined Earth-abundant metal catalyst, [(^2,6-iPr₂PhBDI)Mn(μ-H)]₂, has been found to couple organosilanes to diamines to prepare networks that feature varied silane substitution and diamine chain lengths. By performing dehydrocoupling in the absence of solvent with 0.01 mol% catalyst loading, substrate utilisation turnover frequencies of up to 300 s⁻¹ have been achieved at early reaction times, the highest Si–N dehydrocoupling activity to be observed on a per catalyst basis. These networks have been employed as absorbents for common organic solvents, a property that had not been studied for this class of materials. By incorporating a long-chain hydrophobic linker, one network has been found to absorb 7.7× its original mass in THF and recycling has been demonstrated upon solvent removal. Controlling the degree of dehydrocoupling also offered an opportunity to deposit coatings from freshly-prepared silane diamine polymer solutions and monitor their integrity upon curing in air. While uniform and persistent coatings have been obtained from 1,6-diaminohexane derived polymers, the need to prepare dilute solutions that have a short shelf-life and the tackiness associated with extended dry times have been identified as potential limitations.

中文翻译：

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硅烷二胺共聚物：高效合成、溶剂吸收能力和作为涂料的局限性

尽管硅烷二胺共聚物已经引起了催化界的关注，但其合成和最终用途的优化仍有待探索。在这项研究中，我们发现一种明确的地球丰富金属催化剂 [( ^{2,6-iPr ₂ Ph} BDI)Mn(μ-H)] ₂可以将有机硅烷与二胺偶联，以制备具有不同硅烷取代的网络和二胺链长。通过在没有溶剂的情况下以0.01 mol%催化剂负载量进行脱氢偶联，在反应早期就实现了高达300 s ^-1的底物利用周转频率，这是在每种催化剂的基础上观察到的最高Si-N脱氢偶联活性。这些网络已被用作常见有机溶剂的吸收剂，这一特性尚未针对此类材料进行研究。通过加入长链疏水性连接体，一种网络在 THF 中的吸收量是其原始质量的 7.7 倍，并且在溶剂去除后可循环利用。控制脱氢偶联程度还提供了从新鲜制备的硅烷二胺聚合物溶液沉积涂层并监测其在空气中固化时的完整性的机会。虽然由 1,6-二氨基己烷衍生的聚合物获得了均匀且持久的涂层，但需要制备具有较短保质期的稀溶液以及与延长干燥时间相关的粘性已被认为是潜在的限制。