Formation of Triple‐Stranded Dinuclear Helicates with Dicatecholimine Ligands: The Influence of Steric Hindrance at the Spacer

A series of new imine-bridged dicatechol ligands 3a–f-H4 with sterically demanding groups at the spacers are used for the formation of titanium(IV) complexes M4[(3)3Ti2]. All three ligands 3a–c-H4 form triple-stranded dinuclear helicates. When the bulky ligands 3a-H4 or 3c-H4 are used with potassium as the countercation, oligomeric or polymeric side products are also observed. The imine-bridged ligand 3e-H4 quantitatively forms helicates M4[(3e)3Ti2] and not a M4L6 tetrahedron as observed with Raymond’s analogous amide-bridged dicatechol ligand 3i-H4. NMR spectroscopic investigations at variable temperature show that ligand 3f-H4, which possesses a spiro fluorenyl group at the central unit …