Cyclopentadienes containing one or two (perfluorooctyl)ethyldimethylsilyl groups and a trimethylsilyl or trimethylstannyl group were prepared by the reaction of C 8 F 1 7 CH 2 CH 2 Si-(CH 3 ) 2 Cl with LiC 5 H 5 (C 5 H 5 Si(CH 3 ) 2 CH 2 CH 2 C 8 F 1 7 , 1; C5H4{Si(CH3) 2 CH 2 CH 2 C 8 F 1 7 } 2 , 2) or with LiC 5 H 4 Si(CH 3 ) 3 (C 5 H 4 {Si(CH 3 ) 2 CH 2 CH 2 C 8 F 1 7 }{Si(CH3) 3 }, 3) or by the reaction of 1 with butyllithium followed by (CH 3 ) 3 SnCl addition (C 5 H 4 {Si(CH3) 2 CH 2 CH 2 C 8 F 1 7 }{Sn(CH 3 ) 3 }, 4). All the cyclopentadienes were found, in analogy with similar known compounds, to be mixtures of isomers between which prototropic and on the NMR time scale fast metallotropic shifts occurred, as confirmed by variable-temperature 1 H and 1 3 C NMR. The reaction of 4 with TiCl 4 gave Ti(IV) complex [{η 5 -C 5 H 4 Si(CH3) 2 CH 2 CH 2 C 8 F 1 7 }TiCl 3 ] (5), whereas the reaction of [(C 5 H 4 SiMe 3 )TiCl 3 ] with lithium salts of 1 and 2 yielded complexes [η 5 -C 5 H 4 Si-(CH 3 ) 2 CH 2 CH 2 C 8 F 1 7 }{η 5 -C 5 H 4 Si(CH3) 3 }TiCl 2 ] (6) and [{η 5 -C 5 H 3 (Si(CH3) 2 CH 2 CH 2 C 8 F 1 7 ) 2 }{η 5 -C 5 H 4 Si(CH 3 ) 3 }TiCl 2 ] (7), respectively. Complex [{η 5 -C 5 H 4 Si(CH3) 2 CH 2 CH 2 C 8 F 1 7 } 2 TiCl 2 ] (8) was synthesized by the reaction of 2 equiv of lithium salt of 1 with TiCl 3 .3THF, followed by PbCl 2 oxidation. An X-ray crystal and molecular structure of titanocene dichloride substituted by fluorous ponytails, 8, was determined. The results show the applicability of fluorous chemistry methodology in early transition metal organometallic chemistry.