Reaction of the amino-alkoxides HOCH(CH2NMe2)2 (Hbdmap) and HOC(CH2NMe2)3 (Htdmap) with [Ti(OR)4] yields a series of heteroleptic titanium alkoxides [Ti(OR)4−n(L)n] (L = bdmap, tdmap). Substitution of the monodentate alkoxide with the chelating alkoxides becomes progressively more difficult, with homogeneous products being obtained only for n = 1, 2. The structure of [Ti(OEt)3(bdmap)]2, a µ-OEt bridged dimer, has been determined. Hydrolysis of [Ti(OR)2(L)2], by adventitious moisture affords the dimeric oxo-alkoxides [Ti(O)(L)2]2, both of which have been characterised crystallographically. These two compounds have also been prepared by reaction of [Ti(NMe2)2(L)2] with the hydrated metal salts [Zn(acac)2·2H2O] and [Zn(OAc)2·2H2O] using the intrinsic water molecules in these salts to react with the labile amido groups, though the former also produces Me(Me2N)C![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
C(H)C(O)Me from reaction of liberated HNMe2 with the coordinated acac ligand, while the latter also affords the ligand exchange product [Zn(OAc)(bdmap)]. In neither case does the free dimethylamino group of [Ti(O)(L)2]2 coordinate a second metal. The dimeric structure of [Zn(OAc)(bdmap)]2 has been established, and the structure of the tetrameric oxo-alkoxide [Ti(O)(OPri)(OCH2CH2NMe2)]4 is reported for comparison with others in this study. [Ti(OEt)3(bdmap)]2 has been used as a precursor in AACVD (Aerosol-Assisted Chemical Vapour Deposition) to generate amorphous TiO2 films on glass at 440 °C, and TiO2@C nanoparticles of approximate diameter 350 nm with a carbon coating of width ca. 75 nm on heating in a sealed container at 700 °C.
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