The structural conversion of multinuclear titanium(IV) μ-oxo-complexes.

Abstract

For the first time we report the structural conversion processes of hexanuclear μ-oxo-Ti(IV) complexes into tetranuclear ones. Single-crystal X-ray diffraction studies reveal that metastable hexanuclear μ-oxo complexes ([Ti6O6(O(t)Bu)(O2CR')6]) are formed in the first stage of reactions between [Ti(O(t)Bu)4] and branched carboxylic acids R'COOH (R' = C(Me)2Et, CH2(t)Bu, (t)Bu). In the next stage they convert into tetranuclear μ-oxo-Ti(IV) complexes of the formula [Ti4O4(O(t)Bu)4(O2CR')4]. Spectroscopic investigations ((13)C NMR, IR, and MS) proved that the conversion of hexanuclear clusters relies on the attachment of smaller units (e.g., [Ti3O(O(t)Bu)8(O2CR')2] or [Ti4O2(O(t)Bu)6(O2CR')6]) and intermediate species formation (e.g., [Ti9O8(O(t)Bu)14(O2CR')6]). The decomposition of intermediate systems in the next reaction stage leads to the formation of tetranuclear clusters. The type of solvent used in the synthesis of multinuclear oxo-Ti(IV) complexes is an important factor, which influences the kind of clusters formed.