A series of ponytail-appended arylphosphines P(C6H4R-m)3 (m = 4, R = n-C6F131, n-CH2CH2C6F133, n-C6H134, n-C10H215 or n-C16H336; m = 3, R = n-C6F132) have been studied in the rhodium-catalysed hydroformylation of higher olefins in supercritical CO2 (scCO2), with the perfluoroalkylated ligands exhibiting the highest and the alkylated one the lowest activities. The high rates derived from 1 and 2 probably originate from the strong electron-withdrawing effect of their ponytails, while the slow rates observed with 4–6 are mainly due to the low solubility of these ligands in scCO2.
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