Fluorophilic properties of (perfluorooctyl)ethyldimethylsilyl substituted and tetramethyl(perfluoroalkyl) substituted cyclopentadienes and their Ti(IV), Rh(III), and Rh(I) complexes

Fluorous partition coefficients in perfluorohexane/toluene system for 37 fluorinated silylcyclopentadienes, titanium(IV) complexes derived from them, perfluoroalkyl substituted tetramethylcyclopentadienes, and their Rh(III) and Rh(I) complexes were determined. Specific fluorophilicity and fluorousness according to Kiss and Rábai were calculated for each compound with the help of molecular volume computed with the Gaussian program. The results show relative unimportance of fluorine content parameter for fluorophilicity as shown by a rhodium(I) complex being fluorophilic at fluorine content as low as 46.3%. As expected, fluorophilicity increased with the fluorous ponytail length and ponytail number in series of similar compounds, whereas polar M–Cl bonds were decreasing it. Fluorophilicities of tetramethyl(perfluoroalkyl)cyclopentadiene tautomers varied considerably despite only small differences in molecular volume being found. Most of the compounds were prepared previously, several new silylcyclopentadienes and titanium(IV) silylcyclopentadienyl complexes are reported here for completion.