Porphyrin Complexes of Platinum(II), Platinum(III),
and Platinum(IV): Synthesis and Properties

E. Yu. Tyulyaeva, T. N. Lomova, and L. G. Andrianova

Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia

Received December 30, 1999

Abstract—Complexing mesotetraphenylporphine H₂TPP with K₂[PtCl₆] in boiling pyridine or with K₂[PtCl₄]
in boiling benzonitrile produces stable platinum complexes of composition (Cl)₂Pt^IVTPP or Pt^IIITPP. Reacting
mesoporphyrin dimethyl ether H₂MP with K₂[PtCl₆] in boiling pyridine yields (Cl)Pt^IIIMP, a complex in which
platinum has an unusual oxidation number. The complexes are identified using UV and IR spectroscopy, by
atomic adsorption spectrometry, and by quantitative analysis. The species of the complexes existing in mixed
H₂SO₄-containing proton-donating solvents are discovered. The kinetics of the dissociation of metal porphyrins
for various solvent acidities and temperatures are determined. The complexes are soluble in concentrated
H₂SO₄ in the molecular form or in the form of an ion–molecule association species with the proton of the sol-
vent. The stability, solute species, and the mechanism of dissociation of the metal porphyrin are controlled by
the presence or absence of an acido ligand in the first coordination sphere and by the configuration of the mac-
rocycle.

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