H. Sugimoto, N. Ueda, M. Mori
Nov 1, 1981
Citations
0
Influential Citations
32
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
Tervalent cobalt complexes of octaethylporphyrin (OEP) and tetraphenylporphyrin (TPP), [CoIII(OEP)(H2O)2]X (X=ClO4, BF4), [CoIII(OEP)(THF)2]ClO4, [CoIII(TPP)(H2O)2]X (X=ClO4), and [CoIII(TPP)(H2O)Y] (Y=Cl, Br, SCN, N3) were synthesized. Molecular weight measurements indicate that only [CoIII(TPP)(H2O)2]BF4 and [CoIII(TPP)(H2O)2]ClO4 aggregate at higher concentrations in chloroform. In polar solvents such as methanol, all are monomeric. In nonpolar solvents, all the complexes show Soret bands at shorter wavelengths and somewhat paramagnetic 1H NMR spectra; these anomalies are absent in polar solvents. Tetrafluoroborates and perchlorates react with ethyl vinyl ether smoothly to form 2,2-diethoxyethylcobalt(III) complexes which are easily converted to formylmethylcobalt(III) complexes. 1H NMR and absorption spectra of the amine adducts prepared in this study, [CoIII(OEP)(L)2]ClO4 (L=pyridine, 2-methylimidazole) and [CoIII(TPP)(L′)2]ClO4 (L′=pyridine, 4-cyanopyridine, 4-methylpyridine), indicate that the two ...