Direct Quantitative Estimation of the Macrocyclic Effect in the Dissociation of Protoporphyrin Complexes

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(Chloro)platinum(III)protoporphyrin and its closest noncyclic analogue, platinum(III)biliverdin, are synthesized; the forms and stability of the complexes in proton-donating solutions as dependent on temperature and solvent composition are studied. The macrocyclic effect (the effect of coordinated macrocyclic ligand opening) is directly estimated quantitatively; a correlation between its contribution to the rate of dissociation (or stability) of the complexes and their structures is found.

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