BALANTSEVA et al.
Acknowledgements
pyridine by NiTPP in chloroform and benzene
are 2.19–3.01 and 1.85–3.15, respectively (the devia-
tions of lgK depend on the method of defining the con-
stants). The Ni(II) complexes of the natural porphyrins
form stable solvates with pyridine [10]. Formation of
bi-pyridine nickel porphyrinate NiTPP(CN)4(Py)2 was
established in work [31]. On the other hand the results
of calorimetric measurements obtained in article [32]
show the binding saturation of NiP complex. It is inter-
esting that the main reasons causing the weak binding
unsaturation of the Ni2+ ions in NiP are the effects of
alkyl substitution just like in the case of the decrease of
Mn and Zn crystal solvates stability. This seeming con-
tradiction is explained by the need to take into account a
presence of the opposite p-dative Ni®Npy bond, that is
absent in (Ac)MnP and ZnP. As a result, the opposite
p-dative interaction of nickel ion with macrocycle in
NiP–Py complex weakens due to +I-induction effect of
t-butyl substitutes. On the other hand the steric factor
leads to distortion of the plane structure causing the
metal to leave the coordinating cavity of chromophore.
Both of these factors lead to weakening of metal cation
and porphyrin anion interaction and increase of the
binding unsaturation of cation.
We would like to thank A. S. Semejkin for granting the
tetrakis(3,5-di-t-butylphenyl)porphin.
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