A new method for the repetitive batch silylative coupling (trans-silylation) of vinylsilanes with vinyl boronates in the presence of Ru(CO)Cl(H)(PCy₃)₂ immobilized in poly(ethylene glycols) (PEGs) has been developed. Three PEGs (PEG600, PEG2000, and MPEG2000) with different molecular weights and end groups (MW = 600–2000) were tested as solvents and immobilization media, while an aliphatic solvent (n-hexane or n-heptane) or supercritical CO₂ was used for product extraction. By applying 2 mol % of the Ru–H catalyst, it was possible to carry out up to 15 complete runs, with the predominant formation of 1-boryl-1-silylethenes. This immobilization strategy permitted for catalyst reuse and obtaining higher TON values (approximately 660–734) compared to the reaction in conventional solvents (∼50). Detailed kinetic studies of the most effective catalytic system were performed to determine catalyst activity and stability. Moreover, the reactions were carried out in an MPEG2000/scCO₂ biphasic system, positively influencing the process sustainability.

中文翻译：

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绿色溶剂：PEG和scCO ₂在单相或双相催化体系中，用于乙烯基硅烷与硼酸乙烯基酯向1-Boryl-1-Silylethenes的重复分批偶联

开发了一种新的方法，用于在固定化聚乙二醇（PEG）的Ru（CO）Cl（H）（PCy ₃）₂存在下，乙烯基硅烷与硼酸乙烯基酯进行重复批式甲硅烷基化偶联（反式硅烷化）。三的PEG（PEG600，PEG2000，和MPEG2000）具有不同分子量和端基（MW = 600-2000）进行测试作为溶剂和固定媒体，而脂族溶剂（ñ己烷或ñ庚烷）或超临界二氧化碳₂用于产品提取。通过使用2 mol％的Ru-H催化剂，最多可以进行15次完整操作，并且主要形成1-硼基-1-甲硅烷基。与常规溶剂中的反应（〜50）相比，这种固定化策略允许催化剂重复使用并获得更高的TON值（约660–734）。对最有效的催化体系进行了详细的动力学研究，以确定催化剂的活性和稳定性。此外，反应在MPEG2000 / scCO ₂双相系统中进行，对过程的可持续性产生了积极影响。