Synthesis and Spectral and Coordination Properties of Perhalogenated Tetraphenylporphyrins

The reaction of [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) with N-halosuccinimides in chloroform-methanol, chloroform-butan-1-ol, or DMF gave [2,3,7,8,12,13,17,18- octachloro(bromo)-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) which were treated with trifluoroacetic acid to obtain the corresponding free porphyrin ligands. The synthesized compounds and their dianions were studied by electronic absorption and H-1 NMR spectroscopy and mass spectrometry. The kinetic parameters of the complexation of these ligands with zinc in the systems acetonitrile-Zn(OAc)(2) and acetonitrile-Zn(OAc)(2)-1,8-diazabicyclo[5.4.0]undec-7-ene in the temperature range 298-318 K were determined.