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1.
O. A. Petrov G. V. Osipova O. V. Gornukhina 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2017,91(3):476-481
The state of tetra(1,2,5-thiadiazolo)porphyrazine in a dimethyl sulfoxide medium is investigated. Relatively high stability is observed for the resulting proton-transfer complex, and a chemical structure is proposed for it. It is shown that the nature of the substituent in the porphyrazine macrocycle influences the kinetic parameters of the destruction of tetra(1,2,5-thiadiazolo)porphyrazine, tetra(5-tert-butylpyrazino) porphyrazine, octaethyltetrapyrazinoporphyrazine, and octaphenyltetrapyrazinoporphyrazine in a nitrogen-containing base–dimethylsulfoxide system. The effect the NH acidity of the porphyrazine macrocycle and the nature of the nitrogenous bases have on the reaction rate and activation parameters of the destruction of β,β-annelated porphyrazine proton-transfer complexes is established. 相似文献
2.
The photogeneration of the singlet molecular oxygen (1O2) by copper tetra(4-tert-butyl) phthalocyanine in organic solvents of different nature was substantiated. The apparent quantum yields of 1O2in benzene and pyridine were determined. The data obtained indicate an influence of the coordinating properties of the solvent
on the 1O2yield. However, this factor is not “critical” as in the case of photogeneration of 1O2by copper tetra(5-tert-butylpyrazino)porphyrazine. 相似文献
3.
S. V. Efimova A. B. Korzhenevskii O. I. Koifman 《Russian Journal of General Chemistry》2008,78(8):1622-1625
Quanitative spectral characteristics of Cu, Co, Zn, and Ni tetra(6-tert-butyl-2,3-quinolino)porphyrazine complexes prepared for the first time and soluble in hydrophobic liquids were measaured. Analogous spectral data of the protonated forms of complexes dissolved in sulfuric acids were also evaluated. 相似文献
4.
O. A. Petrov E. L. Kuzmina V. E. Maizlish A. V. Rodionov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2014,88(1):7-11
The acid-basic interaction between tetra(4-nitro-5-tert-butyl)phthalocyanine and pyridine, 2-methylpyridine, morpholine, piperidine, n-butylamine, diethylamine, and triethylamine in benzene is studied. It is found that the intermolecular transfer of protons of NH groups from tetra(4-nitro-5-tert-butyl)phthalocyanine to morpholine and diethylamine is characterized by unusually low values of the reaction constant rates. The effect of the structure of tetra(4-nitro-5-tert-butyl)phthalocyanine and tetra(3-nitro-5-tert-butyl)phthalocyanine, and of the nature of the base on the kinetic parameters of acid-base interaction is demonstrated. A structure is proposed for complexes with the transfer of displaced phthalocyanines’ protons. It is found that they undergo decomposition over time. 相似文献
5.
Cross cyclotetramerization of bis(4-tert-butylphenyl)fumaronitrile with 1,2,5-selenadiazole-3,4-dicarbonitrile in the presence of magnesium butoxide as template afforded a mixture of magnesium(II) porphyrazine complexes, from which magnesium complex of 5,6,8,9,11,12-hexakis(4-tert-butylphenyl)[1,2,5]selenadiazolo[3,4-b]porphyrazine was isolated by column chromatography and was subjected to demetalation on treatment with trifluoroacetic acid. The free ligand was found to undergo protonation at one meso-nitrogen atom in acid medium and deprotonation of one pyrrole ring to form monoanion by the action of bases. Reductive deselenation of the title compound with formation of vicinal diamino porphyrazine was studied by spectral and kinetic methods, and a mechanism involving two hydrosulfide ions was proposed. 相似文献
6.
The kinetics of the reaction of acid-base interaction of tetra(3-nitro-5-tert-butyl)phthalocyanine with cyclic and acyclic nitrogen-containing bases in benzene was studied. The process is found to proceed with a low rate. The schemes of acid-base interaction are proposed and the probable structure of the proton transfer complexes of tetra(3-nitro-5-tert-butyl)phthalocyanine are discussed. The effect of the nature of the nitrogencontaining base on the kinetic parameters of the process is revealed. 相似文献
7.
S. V. Efimova A. B. Korzhenevskii O. I. Koifman 《Russian Journal of General Chemistry》2008,78(8):1614-1621
Complexes of tetra(6-tert-butyl-2,3-quinolino)porphyrazine with Cu, Co, Zn, and Ni soluble in hydrophobic liquids were synthesized for the first time by template tetramerization of derivatives of 6-tert-butylquinoline-2,3-dicarboxylic acid formed from the corresponding acid in the course of carbamide synthesis in presence of the bivalent metal ions. 相似文献
8.
S. V. Efimova A. B. Korzhenevskii O. I. Koifman 《Russian Journal of General Chemistry》2008,78(7):1447-1451
Tetra(6-tert-butyl-2,3-quinoxalino)porphyrazine and its complexes with bivalent metals were synthesized for the first time by template tetramerization of 6-tert-butylquinoxaline-2,3-dicarbonitrile. The obtained macrocyclic compounds are soluble in hydrophobic solvents. Their electronic absorption spectra in organic solvents and the spectra of the corresponding protonated forms in sulfuric acid were studied. 相似文献
9.
G. R. Berezina T. A. Rumyantseva V. P. Kulinich G. P. Shaposhnikov 《Russian Journal of Coordination Chemistry》2011,37(10):796-799
An analysis of the electronic optical properties and solubility in chloroform and DMF of the erbium and ytterbium complexes
with porphyrazine and its octaphenyl- and octa(p-alkylsulfamoylphenyl)-substituted derivatives and tetrapyrazinoporphyrazine and its octaethyl-, tetra(tert-butyl)-, and octaphenyl-substituted derivatives is presented. The dependence of the electronic optical properties and solubility
on the composition of the macrocycle of the studied complexes, namely, on the nature of the extraligand and peripheral environment
of the porphyrazine macrocycle, is shown. 相似文献
10.
O. A. Petrov A. V. Glazunov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2006,80(9):1411-1416
The kinetics of acid-base interaction between tetra(3-nitro-5-tert-butyl)phthalocyanine and cyclic and acyclic nitrogen bases in benzene was studied. The reaction was found to occur with a low rate. The structure and reactivity of protolytes were shown to be interrelated. The structure and stability of the proton-transfer complexes formed are considered. 相似文献
11.
A. A. Gaberkorn M. -P. Donzello P. A. Stuzhin 《Russian Journal of Organic Chemistry》2006,42(6):929-935
Cross cyclotetramerization of 1,2,5-thiadiazole-3,4-dicarbonitrile and 4-tert-butylphthalodinitrile in the presence of magnesium butoxide gave a mixture of symmetric and asymmetric porphyrazine magnesium(II) complexes. One of these, (22(3),72(3),122(3)-tri-tert-butyltribenzo[b,g,l][1,2,5]thiadiazolo[3,4-q]-5,10,15,20-tetraazaporphyrinato)magnesium(II) (MgSBBB), was isolated by column chromatography and was treated with trifluoroacetic acid to obtain the corresponding free ligand (H2SBBB). The effect of the mode of heteroring fusion on the electronic absorption spectra of tribenzoporphyrazines was studied. 相似文献
12.
A. V. Rodionov V. E. Maizlish G. P. Shaposhnikov 《Russian Journal of General Chemistry》2016,86(1):96-101
The interaction of 4-tert-butyl-5-nitrophthalonitrile with a series of metal acetates has yielded the corresponding metal phthalocyaninates. The treatment of magnesium tetra(4-tert-butyl-5-nitro)phthalocyaninate with hydrochloric acid has afforded tetra(4-tert-butyl-5-nitro)phthalocyanine. Spectral properties of the prepared macrocycles have been studied. The nature of the organic solvent and the complex forming metal marginally affect the position of the Q band in the electron absorption spectra of the studied compounds. It has been demonstrated that the prepared phthalocyanines can dye polymer materials and are catalytically active towards oxidation of a model sulfur-containing compound. 相似文献
13.
G. P. Shaposhnikov V. P. Kulinich R. P. Smirnov 《Chemistry of Heterocyclic Compounds》1986,22(5):492-494
The syntheses of tetra, 1, 4-dithiacyclohexene)porphyrazine and its lithium salt, obtained by reaction of 3,6-dithiahexene-1,2-dicarbonitrile with lithium amylate, are described. A series of metal complexes of tetra(1,4-dithiacyclohexene)porphyrazine has been synthesized starting from 3,6-dithiacyclohexene-1,2-dicarbonitrile and the salts of the corresponding metals as well as from the free ligand and metal chlorides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 603–606, May, 1986. 相似文献
14.
E. S. Taraimovich P. A. Stuzhin O. I. Koifman 《Russian Journal of General Chemistry》2013,83(2):392-397
Acid-base properties of Al(III), Ga(III), and In(III) complexes with tert-butyl-substituted thianaphthene-annulated porphyrazine and tetra(2,3-pyrazino)porphyrazine in proton-donor medium (CH2Cl2-CF3COOH) were studied by spectrophotometric titration. The concentration stability constants of the singly protonated complexes were determined. The effects of the metal nature and aromatic heterocyclic fragment on the basicity of meso-nitrogen atoms were analyzed. Negative inductive effect of the sulfur atom in the thianaphthene fragment reduces the basicity of the meso-nitrogen atoms as compared to analogous porphyrazine and phthalocyanine complexes. Acid-base transformations of the thianaphthene-annulated tetra(2,3-pyrazino)porphyrazine involve both meso-nitrogen atoms and those in the pyrazine rings. 相似文献
15.
O. A. Petrov G. V. Osipova E. L. Kuz’mina 《Russian Journal of General Chemistry》2011,81(6):1211-1215
The state of tetra(3-nitro-5-tert-butyl)phthalocyanine in DMSO medium was studied. Sufficiently high stability of the obtained proton transfer complex is established,
and its structure is suggested. It is shown that this complex is kinetically unstable in the highly basic media. Effect of
the nature of cyclic and acyclic nitrogen-containing bases on the rate and activation parameters of destruction of the proton
transfer complex of tetra(3-nitro-5-tert-butyl)phthalocyanine was found 相似文献
16.
S. V. Zaitseva S. A. Zdanovich A. S. Semeikin O. I. Koifman 《Russian Journal of General Chemistry》2008,78(3):493-502
Dimeric porphyrin(2,6-bis[15′-(3″,5″-di-tert-butylphenol)-3′,7′,13′,17′-tetramethyl-2′,8′,12′,18-tetraethylporphin-5′-yl]-4-tert-buthylphenol) and its binuclear zinc complex were obtained from 4,4′-dimethyl-3,3′-diethyldipyrrolylmethane, 2,6-diformyl-4-tert-butylphenol and 3,5-di-tert-buthylbenzaldehyde. Coordina-tion properties of dimeric zincporphyrin in the intermolecular reaction with nitrogen-containing bases (imidazole, 2-methylimidazole, and pyridine) in benzene were studied. Geometry and electronic structure of the zincporphyrin and its molecular complexes were calculated by a quantum-chemical method. Energy characteristics of the intermolecular reaction of the dimeric zincporphyrin with bases were determined. The calculated energies of the central metal atom interaction with the nitrogen atom of an extra-ligand agree well with the stability of the Zn-porphyrin molecular complexes. The influence of the deformation distortions of the porphyrin ligand on the strength of the metal-extra-ligand σ-bond was established. 相似文献
17.
O. A. Petrov G. V. Osipova A. S. Semeikin B. D. Berezin 《Russian Journal of Coordination Chemistry》2005,31(12):894-898
Specific features of the acid-base interaction of tetra(4-tert-butyl)phthalocyanine with cyclic and acyclic nitrogen-containing bases in dimethyl sulfoxide are studied. The effect of pK a of proton-withdrawing molecules, basicity of a medium, and steric screening of acidic NH centers on the kinetic parameters of formation of proton-transfer complexes stable in time is shown. 相似文献
18.
A. A. Gaberkorn I. A. Popkova P. A. Stuzhin C. Ercolani 《Russian Journal of General Chemistry》2006,76(9):1494-1503
Basic properties of tri(4-tert-butylbenzo)[b,g,l](1,2,5-thiadiazolo)[3,4-q]porphyrazine and its Cu complex in the H2SO4-CH3COOH medium were studied by means of spectrophotometric titration. It was found that in going from an acetic acid solution 100% H2SO4 the complete acid-base interaction consecutively involves all the four meso-nitrogen atoms of the porphyrazine macroring, as well as one of the nitrogen atoms of the 1,2,5-thiadiazol fragment. The stability constants of the resulting acid forms were determined and compared with the gas-phase proton affinities calculated by the AM1 method. Annulation of a 1,2,5-thiadiazole fragment to the porphyrazine macroring increases the basicity of the 1,2,5-thiadiazole nitrogen atoms and decreases the basicity of macroring meso-nitrogen atoms. 相似文献
19.
《Journal of Inorganic and Nuclear Chemistry》1981,43(8):1803-1806
Dipole moments have been determined for Co(III), Ni(II), Pd(II), Pt(II), Cu(II) and Zn(II) complexes of the fluorinated monothio-β-diketones RC(SH)CHCOCF3 [R 5′-methyl-2′-thienyl, 5′-chloro-2′-thienyl, 4′-isopropylphenyl, 4′-tert-butylphenyl and 3′-fluoro-4′-methoxyphenyl] from static-polarization measurements. The moments clearly indicate cis-square-planar configurations for the nickel, palladium and platinum complexes. The zinc complexes have tetrahedral structure and copper complexes have distorted cis-square-planar structure. The cobalt complexes perhaps have facial-octahedral structure. The values of dipole moment for the complexes varies with R: 5′-methyl-2′-thienyl > 3′-fluoro-4′-methoxyphenyl > 4′-isopropylphenyl ≈ 4′-tert-butylphenyl > 5′-chloro-2′-thienyl. 相似文献
20.
Condensation of phthalimide and 4-tert-butylphthalimide with zinc(II) acetate gave 3-(3-oxo-2,3-dihydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one and 5-tert-butyl-3-(5-tert-butyl-3-oxo-2,3-dihydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one, respectively. Their reactions with 4-phenoxyphthalimide and quinoxaline-2,3-dicarboximide in the presence of Zn(OAc)2 led to the formation of zinc complexes of cis-4,4′-diphenoxytetrabenzoporphyrin and cis-di(4-tert-butylbenzo)diquinoxalinoporphyrin. The complexes were converted into the free bases by treatment with sulfuric acid. Spectral properties of the obtained porphyrin derivatives were studied. 相似文献