Reactions of the fluorous primary phosphines R fn (CH 2 ) 2 PH 2 [R fn ¼ (CF 2 ) n À 1 CF 3 ; n¼ 6, 8, 10] and R fn' CH ¼ CH 2 [(n' ¼ 6, 8, 10) (CH 2 ) 2 ] 2 PCl or R f8 (CH 2 ) 2 PCl 2 , which are characterized in situ. The CF 3 C 6 F 11 /toluene partition coefficients of 4 -9 increase with the number and lengths of the R fn segments.