Carbosilane Dendrons as Solubilizers of Metal Complexes in Supercritical Carbon Dioxide

Palladium complexes of general formula [PdCl2(L)2], 3a−c, were synthesized by reaction of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with the appropriate functionalized phosphine L = [P(C6H5)n((C6H4CH2CH2Si(CH2CH2CH2SiEtMe2)3)3-n)] (n = 2, 2a; 1, 2b; 0, 2c, respectively), which integrated carbosilane dendritic wedges attached to the para-carbon atom of the phenyl group. As a result of the inclusion of the carbosilane dendrons, the solubility of the corresponding palladium complexes 3 in supercritical carbon dioxide (scCO2) was increased in comparison with the palladium complex containing a PPh3 ligand, which showed negligible solubility. The employment of these complexes as precatalysts in a selected Heck coupling reaction in scCO2 was investigated. Good activities were found for 3a−c in such a medium due to the acquired solubility, in contrast with the palladium complex containing PPh3, which showed no activity.