Synthesis, Crystal Structures, and Magnetic and Electrochemical Properties of Highly Phenyl Substituted Trinuclear 5,6,11,12,17,18-Hexaazatrinaphthylene (HATNPh6)-Bridged Titanium Complexes.

Trinuclear titanium complexes coordinated by one ligand with three coordination sites have shown properties of mixed valency and a high number of reversible redox steps. Herein we report on the hexaphenyl-substituted derivative (Cp2Ti)3(μ3-HATNPh6) (2). On reaction of 2 with the ferrocenium salt [Cp2Fe]BF4, the cationic complexes [(Cp2Ti)3(μ3-HATNPh6)] n+ ( n = 1-3; 3-5) become available in a selective way. Cyclic voltammograms show 10 reversible redox states of the trinuclear species 2 without decomposition. In order to classify the degree of electronic communication between the titanium centers, comproportionation constants Kc, IVCT bands in NIR spectra, and magnetic measurements were analyzed. These parameters show strong coupling effects between the titanium centers but no full delocalization. In addition, single-crystal X-ray analysis of the neutral complex 2 and its oxidation products (1+ (3), 2+ (4), and 3+ (5)) revealed the geometric structure of the molecule in the solid state. For the cationic species anion-π interactions between the electron-deficient central ring of the HATNPh6 ligand and BF4- counterions were found.