Interdependence between structure of nitro-substituted palladium and zinc porphyrinates and its spectral, coordination and acid-base properties
| Autor: | Yuliya Ivanova, Oleg A. Golubchikov, Nugzar Zh. Mamardashvili, Alexander S. Semeykin, Dmitry Erzunov, A. S. Vashurin, S. G. Pukhovskaya |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Organic Chemistry chemistry.chemical_element Zinc 010402 general chemistry 01 natural sciences Porphyrin 0104 chemical sciences Analytical Chemistry Coordination complex Inorganic Chemistry Metal chemistry.chemical_compound chemistry Transition metal visual_art Polymer chemistry Electronic effect visual_art.visual_art_medium Nitro Spectroscopy Palladium |
| Zdroj: | Journal of Molecular Structure. 1192:7-14 |
| ISSN: | 0022-2860 |
| DOI: | 10.1016/j.molstruc.2019.04.074 |
| Popis: | Self-porphyrins and corresponding transition metal complexes are used as components of sensory, optically-useful and catalytically active materials. Current work provides data on synthesis and spectrophotometric experiment using meso-dinitrosubstituted derivatives of 5,15-diphenyl-2,3,7,8,12,13,17,18-octaalkylporphyrin being compared with 2,3,7,8,12,13,17,18-octaethylporphyrin and 2,3,7,8,12,13,17,18-octaethyl-5,15-dinitroporphyrin. Influence of macrocycle deformation, nature of metal center, electronic effects of substituents and acidity of medium on coordination and acid-base properties of the porphyrins is analyzed. As result is possible to conclude that the formation of metal porphyrins proceed rather faster in the case of anionic porphyrins than in the case of molecular porphyrins, which is accompanied with the decrease of energy parameters. The process is accompanied with decreasing energy parameters. Significantly increasing acid properties of porphyrin macrocycles are observed upon introducing nitro-groups into meso-positions in contrary to introducing it into para-positions of the phenyl rings. Such transformation results in negligible fall of base properties compared to meso-modification. Reaction of zinc and porphyrins proceeds faster compared to palladium. Moreover, last one is unable to interact with dianionic porphyrin form due to formation of highly stable metal-DBU coordination complex. |
| Databáze: | OpenAIRE |
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