The concept of fluorous biphasic separation has been applied in the recycling of rhodiumbased catalysts for the hydrosilylation of 1-alkenes and fluorinated 1-alkenes by following two approaches. Hydrosilylation of 1-hexene using various silanes and fluorous versions of) in fluorous biphasic solvent systems afforded the corresponding n-hexylsilanes in high yield. The catalyst activities were similar to those obtained using conventional [RhCl(PPh 3 ) 3 ]. The fluorous phase containing the catalyst was recycled at least twice without noticeable loss of activity, despite the fact that 12 and 1.7% of [Rh] was lost for 1 and 2, respectively, in the first cycle. The fluorous hydride intermediate) was identified by NMR spectroscopy. In a reverse approach, the original Wilkinson's catalyst was used for the hydrosilylation of 1H,1H,2H-perfluoro-1-alkenes in benzene or toluene as solvent. Fluorous extraction of the products enabled recycling of the nonfluorous catalyst.
The universal model for predicting lipophilicity based on the mobile order and disorder (MOD) solution thermodynamics was used for the successful prediction of the partition coefficient of 88 fluorous and nonfluorous chemicals in fluorous biphasic PFMCH/toluene and FC-72/benzene binary solvent systems at 25 °C. A general thermodynamic expression aimed to calculate the distribution of substances in any fluorous biphasic system at any temperature is presented. Interestingly, the predictive expression requires the knowledge of only the molar volume and the nonspecific cohesion parameter of the solute allowing valuable estimation of log P of nonexisting fluorous molecules. The present partition model predicts that grafting more and/or longer perfluoroalkyl tails on a given substance does not automatically result in higher partition coefficients.
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