Yeni bir ligand sentezi ve kompleks formasyonlarının incelenmesi

Abstract

Bu çalışmada, literatürde bulunmayan yeni bir makrosiklik vic- dioksim ile transisyön metal kompleksleri elde edilmiştir. Bu yeni ligand; dibenzo (e,k)-2,3-bis(hidroksimino)-l,4-diaza-7,10-ditiyo-2,3,8,9-tetrahldrosiklo- dodesin'dir. o Diklor antiglioksim metilenklorürlü ortamda -5 C de 1 N Na2_CO3" ile muamele edilerek siyanogen-di-N-oksid çözeltisi elde edilmiştir (Grundman ve diğ.). 0 C nin üzerindeki sıcaklıklarda patlayarak bozunan madde, -10 C de l,2-bis(o-aminofeniltiyo)etanın metilenklorürlü çözeltisine ilave edilerek bu sıcaklıkta 10 saat karıştırılmış, bu sayede yeni bir,vic-diok- sim elde edilmiştir. Elde edilen yeni makrosiklik ligand 70 C de alkollü ortamda Ni, Cu ve Co klorürlerin alkollü çözeltisi ile reaksiyona sokularak, renkli iç kompleksler elde edilmiştir. Elementel analiz ve atomik absorbsiyon so nuçları, kompleks oluşumunun metal/ligand oranı(l/2) olacak tarzda vuku- bulduğunu göstermiştir. Yeni ligand ve kompleksler H-NMR, IR,UV-VIS ve Atomik absorbsiyon spektroskopisi teknikleri ile incelenmiş, elementel analizleri alınmıştır. The synthesis and complex formation of various vic-dioximes have been the subject matter of great interest. X-Ray structural analysis of Co (II) and Co (III) complexes of diaminoglyoxime has shown interesting features of vic-dioximes. The anti- and amphi- stereoisomers and their complexes of l,4-diphnyl-2,3-bis(hydroximino)piperazine, bis (oG-mercapto- pyr idyl) glyoxime and 1, 3-diphenyl-2-thiooxo-4, 5-bis (hydroxlmino) imidazoli ne have been isolated (Gök and Bekâroğlu, 1981 - Gök and Serin, 1987). Transition metal complexes of some macrocyclic vic-dioximes have been in this work. For this purpose, antl-dichloroglyoxime is used as an effi cient reacta*t. It reacts with the compound containing NH groups by eli mination of HC1. As a funclional reactant, anti-dichloroglyoxime is also useful in the synthesis of cyclic compounds. In an early work (Gök and Serin, 1987) a new cyclic compound, was obtained with the reaction of N.N'-diphenylethylenediamine and 2-mercaptopyridine with cyanogen-di-N -oxide, which was prepared from anti-dichloroglyoxime and Na"CO_. In this study, we describe the synthesis of a new macrocyclic dioxim- es drived from the reaction of anti-dichloroglyoxime and 1,2-bis (o-amino- phenyltio) ethane group on the chain in order to investigate the effect of the macrocyclic group and complex formation of the vic-dioximes. Cu(II),Ni(II), Co(IJ), complexes of these dioximes are described and their steructures are compared with the previously reported complexes of vari ous vic-dioximes. The cyclization reaction between anti-dichloroglyoxime and 1,2-bis (o-aminophenyltio) ethane is essentially untemplated. Solid NaHCO- is used in order to neutralize, HC1 formed. Since strong based such as Na_CO, ca use the elimination of HC1 from anti-dichloroglyoxime and the formation of a very unstable compound, (Grundmann and others, 1965). In the H-NMR spectrum of 1,2-bis (o-aminophenyltio) ethane, there is one single at 3.50 ppm for primary amine protons. After the cyclization reaction, the singlet at 3.50 ppm disappears and a new band at 8.30 ppm