Synthesis and physicochemical properties of tin(IV), zirconium(IV), and hafnium(IV) 2(3),9(10),16(17),23(24)-tetrakis-(4-tritylphenoxy)phthhalocyaninates

Abstract

The reaction of 4-tritylphenoxyphthalonitrile with SnCl2, ZrCl4 and HfCl4 in the presence of urea under ammonium molybdate catalysis was used to synthesize tetrakis-(4-tritylphenoxy)phthalocyaninates of tin(IV), zirconium(IV), and hafnium(IV). The complexes were characterized by spectral methods of analysis, including mass spectrometry, 1Н NMR, vibrational and electron spectroscopy. All of them form J -type dimer associates in chloroform at concentrations up to ~1.5×10-6 mol/L and lower, are not associated in a mixture of toluene and pyridine up to concentrations of ~3×10-5 mol/L and higher, have catalytic activity in electroreduction reactions of molecular oxygen. The complexes of zirconium and hafnium showed the highest activity. Tin and zirconium complexes are thermally stable in an inert atmosphere up to a temperature of 200°C.