In an effort to generate single-source precursors for the production of metal-siloxide (MSiOx) materials, the tris(trimethylsilyl)silanol (H-SST or H-OSi-(SiMe3)(3 )(1) ligand was reacted with a series of group 4 and 5 metal alkoxides. The group 4 products were crystallographically characterized as [Ti(SST)(2)(OR)(2)] (OR = OPri (2), OBut (3), ONep (4)); [Ti(SST)(3)(OBun)] (5); [Zr-(SST)2 (OBut )(2)(py)] (6); [Zr(SST)(3)(OR)] (OR = OBut (7), ONep, (8)); [Hf(SST)(2)(OBut)2] (9); and [Hf(SST)(2)-(ONep)(2)(py)(n)] (n = 1 (10), n = 2 (10a)) where OPri = OCH(CH3)(2), OBut = OC(CH3)(3), OBun = O(CH2)(3)CH3, ONep = OCH2C(CH3)(3), py = pyridine. The crystal structures revealed varied SST substitutions for: monomeric Ti species that adopted a tetrahedral (T-4) geometry; monomeric Zr compounds with coordination that varied from T-4 to trigonal bipyramidal (TBPY-5); and monomeric Hf complexes isolated in a TBPY-5 geometry. For the group 5 species, the following derivatives were structurally identified as [V(SST)(3)(py)(2)] (11), [Nb(SST)(3)(OEt)(2)] (12), [Nb(O)(SST)(3)(PY)] (13), 2[H][(Nb(mu-O)(2)(SST))(6)(mu(6)-0)] (14), [Nb8O10(OEt)(18)(SST)(2)center dot 1/5Na(2)O] (15), [Ta(SST)(mu-OEt)(OEt)(3)](2) (16), and [Ta(SST)(3)(OEt)(2)] (17) where OEt = OCH2CH3 . The group 5 monomeric complexes were solved in a TBPY-S arrangement, whereas the Ta of the dinculear 16 was solved in an octahedral coordination environment. Thermal analyses of these precursors revealed a stepwise loss of ligand, which indicated their potential utility for generating the MSiOx materials. The complexes were thermally processed (350-1100 degrees C, 4 h, ambient atmosphere), but instead of the desired MSiOx , transmission electron microscopy analyses revealed that fractions of the group 4 and group 5 precursors had formed unusual metal oxide silica architectures.