Application of Green Solvents: PEG and scCO(2) in the Mono- or Biphasic Catalytic Systems for the Repetitive Batch Coupling of Vinylsilanes with Vinyl Boronates toward 1-Boryl-1-silylethenes

[Image: see text] A new method for the repetitive batch silylative coupling (trans-silylation) of vinylsilanes with vinyl boronates in the presence of Ru(CO)Cl(H)(PCy(3))(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 CO(2) 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/scCO(2) biphasic system, positively influencing the process sustainability.