The syntheses and structures of zirconium and titanium complexes containing the novel chelating trisilane-1,3-diolate ligand [Me2Si(R2SiO)(2)](2-) (R = SiMe3) (5)-H-2 are reported. The chloride complexes [Me2Si(R2SiO)(2)]TiCI2 (7a) and [Me2Si(R2SiO)(2)]ZrCI2.2THF (7b) were prepared by the reaction of MCI4 (M = Ti, Zr) with [Me2Si(R2SiO)(2)]TiCl2 (6a) and [Me2Si(R2SiO)(2)](2)Zr (6b), which are derived from the reaction of 5 with M(NEt2)(4), respectively. In the presence of TiCI4, complexes 6a and 7a undergo a ring-opening reaction to produce the dinuclear complex [Me2Si(R2SiO)(2)][TiCI3](2) (9). [Me2Si(R2SiO)(2)]TiMe2 (10) and [Me2Si(R2SiO)(2)]TiBnZ(2) (11) were prepared in moderate yields from reactions of 7a with 2 equiv of MeMgBr and BnzMgCI, respectively. According to NMR spectroscopic investigations, the reaction of the dimethyltitanium complex 10 with B(C6F5)(3) led to full exchange of both methyl groups by C6F5 groups under quantitative formation of [Me2Si(R2SiO)(2)]Ti(C6F5)(2) (12) and a mixture of B(C6F5)(3-n)Me-n, where n = 1-3. The structure of 12 is further evidenced by the preparation of an identical sample from the reaction of 7a with 2 equiv of C6F5MgBr. Refluxing an ether solution of 12 surprisingly gave [Me2Si(R2SiO)(2)](2)TiC6F5](2)O (13) as a result of ether cleavage. The structures of the complexes 7a, 7b, 9, 10, and 13 were determined by X-ray crystallography, and structural discussion of the bond parameters will be given.