Chemistry on the Complex: Derivatization of TiO₄ N₂ -Based Complexes and Application to Multi-Step Synthesis

The chemistry on octahedral TiO₄ N₂ -complexes is described. The Ti(IV)-based precursors are composed of two 3,3'-diphenyl-2,2'-biphenolato ligands (1) and one substituted 1,10-phenanthroline ligand (2-5). The application of imine condensation, palladium-catalyzed C-C bond formation or copper-catalysed azide-alkyne cycloaddition allowed the grafting of various new groups onto these species. In particular Sonogashira reactions permitted to observe an excellent conversion of the starting complexes. This systematic study enabled to compile the factors required to preserve the framework of the complexes in the course of a chemical transformation. Thanks to this chemistry realized on the complex, the Ti(1)₂ fragment was used as a protecting group to develop a multi-step synthesis of a bis-phenanthroline compound (12), for which the synthesis without this protection failed. Thus, a dinuclear complex [Ti₂ (1)₄ (12)] was first prepared starting from complex precursor bearing an acetylenic function via a Hay coupling reaction. This was followed by a deprotection step affording 12. Overall, this work illustrates how the Ti(1)₂ fragment could be an useful tool for the preparation of unprecedented diimine compounds.