Further studies on the oxidation state of iron in mu-oxo dimeric phthalocyanine complexes

The reaction with sodium cyanide of the mu-oxo-bridged complex of tetra-4-t ert-butyl-substituted iron phthalocyanine (form '690') and that of the prod uct of its treatment with organic bases such as Py, Im, etc. (form '627') r esult in the formation of the same ferrous bis-cyanide complex Na-2[(PcFeII )-Fe-t(CN)(2)] which can be readily oxidized to the analogous ferric comple x Na[(PcFeIII)-Fe-t(CN)(2)]. Form '690' has been oxidized to the correspond ing ferric mu-oxo complex (form '630'). Data for all mu-oxo-bridged complex es (chemical behavior; electronic, NMR, Mossbauer, X-ray photoelectron and ESR spectra; magnetic susceptibility) are discussed, and based on them, the following structures are proposed: ((HPcFeII)-Fe-t)(2)O (form '690'), H-2[ ((LPcFeII)-Fe-t)(2)O] (form '627') and ((PcFeIII)-Fe-t)(2)O (form '630'). C opyright (C) 1999 John Wiley & Sons, Ltd.