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Reaction of [Cp*TiMe3] with O(SiPh2OH)2 yields the titanium siloxide derivative [Cp*TiMe{(OSiPh2)2O}](1). Complex 1 reacts with H2O to yield the corresponding oxo-titanium derivative [(Cp*Ti{(OSiPh2)2O})2(µ-O)](2). The molecular structure of complex 2 has been established by X-ray diffraction. Complex 1 reacts with triphenylsilanol to give the asymmetric titanium siloxide [Cp*Ti(OSiPh3){(OSiPh2)2O}](3). Treatment of the dinuclear titanium compound [(Cp*TiCl2)2(µ-O)] with an equimolar amount of O(SiPh2OH)2 yields complex [(Cp*TiCl)2{µ-(OSiPh2)2O}(µ-O)](4) in which the disiloxide moiety is bridging two titanium atoms. The structure of 4 has been determined by X-ray diffraction. Reaction of [Cp*TiMe3] with HOSiPh3 yields the titanium triphenylsiloxide [Cp*TiMe2(OSiPh3)](5). Complex 5 reacts with water to yield [{Cp*TiMe(OSiPh3)}2(µ-O)](6). The triflate compound [Cp*Ti(OSiPh3)2(OTf)](7) can be prepared by reaction of 5 with HOTf and triphenylsilanol. We have tested the catalytic activity of some of the complexes in the epoxidation of cyclohexene. [ABSTRACT FROM AUTHOR]