Potansiyel Biyoetkin Oksovanadyum (IV) Kompleksleri

Abstract

Bu çalışmada, azo-5-pirazolon koordine yeni oksovanadyum(IV) bileşiklerinin sentezi ve karakterizasyonu gerçekleştirilmiştir. İlk aşamada ligand olarak kullanmak üzere 4 farklı o-hidroksiaril- substitue (m- H-, Cl-, Br-, CH3-) azo-5-pirazolon bileşiği sentezlenmiştir (2a-d). İkinci aşamada saflaştırılarak yapıları karakterize edilen ligand yapıların, vanadil sülfat pentahidrat bileşiğiyle reaksiyonu sonucu yeni azo-5-pirazolon temelli oksovanadyum(IV) komplekslerinin ilk sentezi gerçekleştrilmiştir. Tüm ligand yapılar ve komplekslerin karakterizasyonunda FTIR, UV-Vis., GC-MS ya da LCMS-ESI, sadece ligandlar için 1H NMR, 13C NMR, 13C NMR-APT ve sadece paramanyetik vanadyum kompleksleri için ESR ve TG/DTG yöntemleri kullanılmıştır. Spektroskopik ve termal çalışmalar ışığında sentezlenen komplekslerin yapıları L: Ligand olmak üzere [VO(L)2].H2O: (3a-c) ve [VO(L)2].CH3OH: (3d) olarak önerilmiştir. Spektroskopik çalışmalar azo-5- pirazolon yapısının iki dişli davrandığını ve metalle koordinasyonu sırasında azo-fenil aromatik halkasındaki -OH ve pirazolon -C=O gruplarıyla etkileştiğini ortaya koymuştur. Komplekslerin elektronik spektrumları, tipik oksovanadyum(IV) kompleksleri gibi yaklaşık 500 nm civarında düşük absorbanslı bir band vermektedir. Termogravimetrik çalışmalar komplekslerin su (3a-c) ve metanol (3d) moleküllerini koordinasyon küresinin dışında bulundurduğunu göstermektedir. Termal çalışmalarda elde edilen kütle kayıpları önerilen kompleks yapılarla uyumlu olup, kompleksler birbirleriyle benzer parçalanmaları göstermektedir. Yeni oksovanadyum(IV) komplekslerinin ESR çalışmaları bozulmuş oktahedral geometrik yapıyı önermektedir.,In this study, synthesis and characterization of azo-5-pyrazolone coordinated new oxovanadium(IV) compounds were performed. Four different o-hydroxyaryl substituted (m- H-, Cl-, Br-, CH3-) azo-5-pyrazolone compounds were synthesized (2a-d) to be used as ligands in the first stage. In the second step, the first synthesis of the new azo-5-pyrazolone based oxovanadium(IV) complexes was carried out by the reaction of structurally characterized ligands with the vanadyl sulfate pentahydrate compound. For the characterization of all ligands and complexes, FTIR, UV-Vis., GC-MS or LCMS-ESI, only for the ligands:1H NMR, 13C NMR, 13C NMR-APT, and only for paramagnetic vanadium complexes: ESR and TG / DTG methods were used. In the light of spectroscopic and thermal studies, the structures of the complexes have been proposed as [VO(L)2].H2O: (3a-c) and [VO(L)2].CH3OH: (3d) and L: Ligand. Spectroscopic studies have shown that azo-5- pyrazolone acted as bidendate and used OH- and pyrazolone -C=O groups in the azophenyl aromatic ring during its coordination with the metal. The electronic spectra of the complexes gave a low intensity band of about 500 nm, such as typical oxovanadium (IV) complexes. Thermogravimetric studies show that the complexes contain water (3a-c) and methanol (3d) molecules outside the coordination sphere. The mass losses obtained in the thermal studies are in accordance with the proposed complex structures and the complexes show similar fragmentations. ESR studies of new oxovanadium(IV) complexes suggest distorted octahedral geometric structure.

In this study, synthesis and characterization of azo-5-pyrazolone coordinated new oxovanadium(IV) compounds were performed. Four different o-hydroxyaryl substituted (m- H-, Cl-, Br-, CH3-) azo-5-pyrazolone compounds were synthesized (2a-d) to be used as ligands in the first stage. In the second step, the first synthesis of the new azo-5-pyrazolone based oxovanadium(IV) complexes was carried out by the reaction of structurally characterized ligands with the vanadyl sulfate pentahydrate compound. For the characterization of all ligands and complexes, FTIR, UV-Vis., GC-MS or LCMS-ESI, only for the ligands:1H NMR, 13C NMR, 13C NMR-APT, and only for paramagnetic vanadium complexes: ESR and TG / DTG methods were used. In the light of spectroscopic and thermal studies, the structures of the complexes have been proposed as [VO(L)2].H2O: (3a-c) and [VO(L)2].CH3OH: (3d) and L: Ligand. Spectroscopic studies have shown that azo-5- pyrazolone acted as bidendate and used OH- and pyrazolone -C=O groups in the azophenyl aromatic ring during its coordination with the metal. The electronic spectra of the complexes gave a low intensity band of about 500 nm, such as typical oxovanadium (IV) complexes. Thermogravimetric studies show that the complexes contain water (3a-c) and methanol (3d) molecules outside the coordination sphere. The mass losses obtained in the thermal studies are in accordance with the proposed complex structures and the complexes show similar fragmentations. ESR studies of new oxovanadium(IV) complexes suggest distorted octahedral geometric structure.