The reaction of dithallium salts of tetramethyldisiloxanediylbis(cyclopentadienyl), 3, and hexamethyltrisiloxanediylbis(cyclopentadienyl), 4, with two equivalents of TiCl 4 gives the title compounds tetramethyldisiloxanediylbis(cyclopentadienyltitanium trichloride), 5 and hexamethyltrisiloxanediylbis(cyclopentadienyltitanium trichloride), 6 respectively. The stoichiometric reaction of 5 and 6 with water results in the formation of new oxygen-bridged metallocenes [(TiCl 2) 2( μ 2-O)-( η 5-C 5H 4) 2- μ 2-(SiMe 2) 2O], 7, and [(TiCl 2) 2( μ 2-O)-( η 5-C 5H 4) 2- μ 2-(SiMe 2) 3O 2}], 8. In addition, further reaction of 7 and 8 with another one equivalent of water or the treatment of 5 and 6 with an excess amount of water gives rise to the formation of the metallocene compounds having Ti 4O 4 rings [(TiCl) 2( μ 2-O)-( η 5-C 5H 4) 2- μ 2-(SiMe 2) 2O] 2( μ 2-O) 2, 9, and [(TiCl) 2( μ 2-O)-( η 5-C 5H 4) 2- μ 2-(SiMe 2) 3O 2] 2 ( μ 2-O) 2, 10. All the new kinds of metalocenes prepared have been characterized by IR, NMR, mass spectrometry, or elemental analysis. Especially an investigation of the Δδ values in 1H NMR and a comparison between the theoretical and observed isotopic ratio in a mass spectra among the synthesized bridged compounds have been very conveniently utilized to study their structures. Polymerization experiments with the dinuclear complexes in the presence of methylaluminoxane as a cocatalyst indicate that the compounds 5 and 6 do exhibit catalytic activity for syndiotactic polymerization of styrene.