The properties of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine in 2-methylpyridine were studied. During the acid-base interaction of molecules, a kinetically stable complex was formed with proton transfer. The addition of morpholine, piperidine, n-butylamine, and diethylamine to 2-methylpyridine led to the destruction of this complex, unlike the addition of tert-butylamine and triethylamine. The influence of the proton-accepting ability and spatial structure of the nitrogen-containing base, as well as the basicity of the medium, on the process of the tetrapyrazinoporphyrazine macrocycle decomposition was considered, and a destruction scheme was proposed.

Reactions between octa(2,6-fluorophenyl)porphyrazine and pyridine, 2-methylpyridine, morpholine, piperidine, butylamine, tert-butylamine, diethylamine, and triethylamine in a benzene medium have been studied. The acid–base reactions between the macroheterocycle and piperidine or butylamine are slow processes leading to the formation of kinetically stable proton-transfer complexes. The structures of these complexes have been optimized using CAM-B3LYP/cc-pVTZ. The changes in the reactivity of octa(2,6-fluorophenyl)porphyrazine are analyzed as a function of the steric structure and proton-acceptor power of the nitrogenous base.

The interaction of the first synthesized tetra-4-chloro-tetra-5(5-methyl-2-isopropylphenoxy)phthalocyanine with pyridine, 2-methylpyridine, morpholine, piperidine, n-butylamine, tert-butylamine, diethylamine, and triethylamine in benzene was studied. The acid–base reaction is one of the rarely observed slow processes that forms kinetically stable proton transfer complexes. The structure of the complexes is described. The reactivity of tetra-4-chloro-tetra-5(5-methyl-2-isopropylphenoxy)phthalocyanine changes depending on the proton-acceptor ability and spatial structure of the nitrogen-containing base.

The catalytic action of the cyclic and acyclic organic nitrogen bases on the complex formation between zinc and tetra(4- tert -buthyl-5-phenylsulfanyl)phtalocyanine in benzene was studied. The acid-base interaction was shown to precede the complexation and to play a key role in it. The scheme of complex formation of zinc with tetra(4- tert -buthyl-5-phenylsulfanyl)phtalocyanine in the system containing also organic nitrogen base and benzene was given. The relationship between catalytic activity of the base and its ability to accept proton as well as structure was described.

The interaction of tetra-4-(2-methoxyphenoxy)phthalocyanine and tetra-4-(3-methoxyphenoxy)phthalocyanine with pyridine, 2-methylpyridine, morpholine, piperidine, n -butylamine, tert -butylamine, diethylamine, and triethylamine in benzene has been studied. The acid–base reaction involving n -butylamine and piperidine is an unusually slow process, leading to the formation of kinetically stable proton transfer complexes. The structure of these complexes is proposed. The change in the reactivity of tetraphenoxy-substituted phthalocyanines depending on the proton-acceptor ability and spatial structure of the nitrogen-containing base is considered. Pyridine, 2-methylpyridine, and morpholine do not form proton transfer complexes because of their weak basicity. A similar picture is observed in the case of tert -butylamine, diethylamine, and triethylamine, which have a more sterically screened nitrogen atom than that in n -butylamine and, as a result, do not react with tetraphenoxy-substituted phthalocyanines.

The effect of cyclic and acyclic nitrogen-containing organic bases on the formation of a zinc complex with tetra(4- tert -butyl-5-phenylsulfanyl)phthalocyanine in benzene has been studied. The acid-base interaction precedes the complex formation and plays a key role in it. The scheme is given for the formation of a zinc complex with tetra(4- tert -butyl-5-phenylsulfanyl)phthalocyanine in the nitrogen-containing base-benzene system. A relationship between the catalytic activity of the base and its proton-acceptor ability and structure is determined.

A study is performed of the state of octa(4- tert -butylphenyl)tetrapyrazinoporphyrazine in dimethyl sulfoxide. It is found that the acid–base interaction of partner molecules creates a time-stable complex with proton transfer. It is shown that adding morpholine, piperidine, n -butylamine, and diethylamine to dimethyl sulfoxide results in destruction of this complex, in contrast to adding pyridine, 2-methylpyridine, tert -butylamine, or tri- n -butylamine. The effect the proton-acceptor ability and the spatial structure of the base have on the decomposition of the tetrapyrazinoporphyrazine macrocycle is considered.

The regularities of the catalytic influence of nitrogen-containing base and DMSO on the formation of porphyrazine complexes with magnesium acetylacetonate and magnesium and zinc acetates in benzene are considered. The acid-base interaction plays a key role in the complex formation process. A relationship between the catalytic activity of the base and its proton-acceptor capacity and structure is shown. The schemes of formation of magnesium and zinc complexes with porphyrazines in a benzene—nitrogen-containing base (DMSO) are presented. The peculiarities of the catalytic effect of DMSO on the reaction of porphyrazines with magnesium acetate in benzene are analyzed.

A study is performed of patterns of the destruction of β-substituted and β,β-annelated porphyrazines in the presence of cyclic and acyclic nitrogen-containing bases in dimethylsulfoxide. Possible schemes of the mechanism are proposed and substantiated. It is shown how the NH acidity of the porphyrazine macrocycle, the spatial structure of the nitrogen-containing base, and its proton-acceptor ability affect the kinetic parameters of destruction. Structural data of proton-transfer complexes in dimethylsulfoxide are discussed.

The properties of octakis(4-tert-butylphenyl)tetrapyrazinoporphyrazine in pyridine have been studied. Acid–base interaction between the partner molecules leads to the formation of a proton-transfer complex. Unlike tert-butylamine and triethylamine, addition of n-butylamine, diethylamine, morpholine, and piperidine promotes decomposition of the proton-transfer complex. The effects of the basicity of the medium, proton-acceptor power, and steric structure of the nitrogen base on the decomposition of tetrapyrazinopor­phyrazine macrocycle have been studied, and a plausible mechanism of the decomposition has been proposed.

The reaction of acid-base interaction of octa(4-tert-butylphenyl)tetrapyrazinophosphyra-zine with pyridine, 2-methylpyridine, morhpoline, pipyridine, n-butylamine, tert-butylamine, diethylamine, triethylamine and dimethylsulfoxide in benzene was investigated. It is shown that the researched porphyrazine forms kinetically stable proton transfer complexes with pyridine, 2-methylpyridine, morpholine and dimethylsulfoxide. In benzene-base system an acid-base equilibrium between the molecular form of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine and its proton transfer complex was established. The interaction of substituted tetrapyrazinoporphyrazine with morpholine in benzene was revealed to be a kinetically controllable process which occurs with low reaction rate and high values of activation energy. Such values are not inherent to most of relatively simple liquid-phase acid-base systems. The kinetic equation of the process was found, and, based on the spectral changes accompanying the reaction, a cheme of two-stage process of proton transfer of NH-groups of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine to morpholine in benzene was proposed. A possible structure of proton transfer complex of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine with organic bases is shown. In these complexes the inner hydrogen atoms of the cycle, bonded with base molecules, lie under and above the plane of the molecule, and the proton transfer from acid to base is limited either by the H-complex or the ion-ion associates constituting an H-bonded ion pair. Depending on the proton accepting tendency of the base, the acid-base equilibrium can shift towards or away from the more or less polarized structure. It was revealed that in benzene - n-butylamine (tri-butylamine, diethylamine, triethylamine, pipyridine) system the acid-base interaction involving octa(4-tert-butyl-phenyl)tetrapyrazinoporphyrazine occurs incredibly fast, with rates not measurable by standard spectrophotography methods. The forming proton transfer complexes are highly labile due to concurrent proton reaction occurring, leading to the formation of dianion form of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine. This form undergoes spontaneous dissolution into low-molecular colorless products due to the lack of compensation of excess charge in the macrocycle.

Study of the acid–base interaction of tetrakis(4- tert -butyl-5-phenylsulfanyl)phthalocyanine with cyclic and acyclic nitrogen bases in benzene and benzene–dimethyl sulfoxide has shown that this very slow interaction leads to the formation of stable proton-transfer complexes. The effects of the solvent polarity and proton-acceptor properties and steric structure of the nitrogen-containing base have been examined.

The regularities of intermolecular proton transfer from β-substituted porphyrazines to dimethylsulfoxide, cyclic and acyclic nitrogen-containing bases in inert solvents are considered. We found that the process rates are unusually low. We showed that the acidic properties of a porphyrazine macrocycle, the proton-acceptor ability of a base, and the dielectric constant of the environment influence the kinetic parameters of acid–base interaction. The structure and the stability of proton transfer complexes of porphyrazines are discussed.

A study is performed for the state of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine in dimethylsulfoxide. The formation of a stable complex with proton transfer is observed. It is shown that addition of n-butylamine and diethylamine to dimethylsulfoxide results in the destruction of this complex and the tetrapyrazinoporphyrazine macrocycle. The effect the tert-butyl substituents in octaphenyltetrapyrazinoporphyrazine have on the kinetic parameters of the process is established.

The acid–base interaction between octa(m-trifluoromethylphenyl)porphyrazine and pyridine, 2‑methylpyridine, morpholine, and piperidine in the benzene–dimethylsulfoxide system is studied. It is found that the intermolecular proton transfer of NH groups from octa(m-trifluoromethylphenyl)porphyrazine to morpholine and piperidine proceeds with unusually low rate constants. It is shown that the β,β-benzoannelation in a porphyrazine macrocycle and the base affect the kinetic parameters of the process. A structure is proposed for the proton-transfer complexes of substituted porphyrazines. It is found that they decompose over time.

The review presents data on the complexation of octa(m-trifluoromethylphenyl)porphyrazine and hexa(m-trifluoromethylphenyl)benzoporphyrazine with zinc acetate in a system nitrogen-containing base - benzene. It was shown that the investigated porphyrazines, having pronounced acidic properties at the incyclic NH bonds, interact with n-butylamine, tret-butylamine, morpholine and piperidine in benzene with the formation of proton-transfer complexes. In these complexes, the intocyclic protons of the NH-groups associated with the oxygen atom of the dimethyl sulfoxide molecule and the intocyclic nitrogen atoms are located above and below the plane of the macrocycle. In an inert, low-polar benzene, the degree of proton transfer from acid to base is limited by the stage of the H-complex (H-associate) formation or ionic complex (ion-ion) associate. It was found that proton transfer complexes of octa(m-trifluoromethylphenyl)porphyrazine and hexa(m-trifluoromethylphenyl)benzoporphyrazine exhibit low kinetic stability. The role of this acid - base interaction in the complexation reaction of octa(m-trifluoromethylphenyl)porphyrazine and hexa(m-trifluoromethylphenyl)benzoporphyrazine with zinc acetate is shown. High kinetic stability of zinc complexes with the investigated porphyrazines in contrast to complexes with proton transfer was revealed. Based on the analysis of kinetic data, it was found that the introduction of Zn2+ into the coordination center of octa(m-trifluoromethylphenyl)porphyrazine and hexa(m-trifluoromethylphenyl)benzoporphyrazine is preceded by the stage of interaction of porphyrazine with a nitrogen-containing base. This leads to the formation of an intermediate reactive acid-base complex that differs in composition from complexes with proton transfer of porphyrazines. It was shown that piperidine and n-butylamine exert the maximum catalytic effect on the formation of zinc complexes with the investigated porphyrazines. A decrease in the pKa of the nitrogen-containing base, as well as an increase in the spatial shielding of the nitrogen atom in the amine by alkyl substituents, counteracts the formation of an intermediate acid-base complex and, as a result, reduces the complexation rate of octa(m-trifluoromethylphenyl)porphyrazine and hexa(m-trifluoromethylphenyl)benzoporphyrazine with zinc acetate in benzene.

The state of tetra(1,2,5-selenodiazolo)porphyrazine in proton-acceptor media of different basicities is studied. It is shown that porphyrazine with selenodiazole rings forms a proton-stable complex with proton transfer in dimethylsulfoxide. Addition of nitrogen-containing bases into dimethylsulfoxide destabilizes this complex, with subsequent destruction of the porphyrazine macrocycle. It is found that the kinetic parameters of the process depend on the pK(a)values of the base, and on the spatial screening of the nitrogen atom in the composition of the molecule.