The synthesis of novel titanoxane compounds, [{(TiCl)(Ti)[mu-(eta(CMe4SiMe2O)-C-5-Me-5-kappa O)](2)(mu-O)}(2)(mu-O)] (4) and [{Ti[mu-(eta(5)-(CMe4SiMe2O)-Me-5-kappa O)](mu-O)}(6)] (5), by controlled hydrolysis of a dinuclear titanium/oxo complex is described. Complexes 4 and 5 show unprecedented structural features for organometallic oxide derivatives of transition elements and represent unique fully characterized examples of tetra- and hexanuclear organo-transition-metal oxide compounds with an open-chain and a monocyclic structure, respectively.