Titanium‐Oxo Clusters with Bi‐ and Tridentate Organic Ligands: Gradual Evolution of the Structures from Small to Big

Homometallic titanium oxo clusters are one of the most important groups of metal oxo clusters, with more than 300 examples characterized by X‐ray structure analyses. Most of them are uncharged and are obtained by partial hydrolysis and condensation of titanium alkoxo derivatives. The cluster cores, ranging from 3 to >50 titanium atoms, are stabilized by organic ligands. Apart from residual OR groups, carboxylato and phosphonato ligands are most frequent. The article critically reviews and categorizes the known structures and works out basic construction principles by comparing the different cluster types.