ÖZET Anahtar Kelimeler: vic-Dioksim, oktil bromür, Nikel(II), Demir(II), Kobalt(II), Uranil (UO2) kompleksleri Oksimlerin, özellikle vic-dioksimlerin geçiş metalleri ile vermiş oldukları komplekslerin önemi büyüktür, dolayısıyla üzerinde yoğun çalışmalar yapılmıştır. Literatürde bilinen makrosiklik yapıdaki vic-dioksim ligantlann sayısı oldukça sınırlıdır. Makro halka bünyesindeki hetero atomlar 0,N,S veya bunların ikili karışımlarından ibarettir. Burada donör grupların türüne bağlı olarak metal iyonlarıyla etkileşim farklılık göstermektedir. Sadece N ve S donör grupları mevcut olduğunda geçiş metalleri ile kompleks oluştururken N ve O karışımından oluşan makro halka sadece alkali metallerle kısmen etkileşmektedirler. Buradan yola çıkarak bu çalışmada önce 2-aminotiyofenol azot atmosferinde oktil bromür ile reaksiyonundan %73 verimle 2-oktilsülfonil aminobenzen bileşiği sentezlenmiş olup bu bileşiğin siyonojen di-N-oksit ile -40°C de reaksiyonu sonucunda oksim türevi (H2L) elde edilmiştir. Elde edilen vic-dioksim bileşiği diklorometan, kloroform ve aseton vb. solventlerde çok iyi çözünmektedir. Son aşama olarak elde edilen bu makrosiklik oksimden Nikel(II), Kobalt(ü), Demir(II) iyonları ile metal ligand oranı 1:2 olan mononükleer, Uranil (UO2) ile metal ligand oram 2:2 olan binükleer kompleksleri izole edilmiştir. Sentezlenen bileşiklerin yapılan IR/H-NMR, MS/F AB, UV-VIS gibi yöntemlerle aydınlatılmıştır. vm
SYNTHESIS AND COMPLEXATTON OF A NEW BRANCHED VIC- DİOKSİME Keyword: vic-dioxime, 2-aminothiophenoi, octyl bromide, 2-octyIsuIfanyI amino benzene, metai oxime complexes (Ni11, Co11, Fe11 and U(>2(n)). The coordination chemistry of vic-dioximates is an intensive area of study and numerous transition metal complexes of this group of ligands have been investigated. The exceptional stability and unique electronic properties of these complexes can be attributed to their planar structure which is stabilized by hydrogen bending. We have long had an interest in the chemical behaviour of complexes containing a planar MN4 core structure and additional donor sites. Although extensively investigated under the facit assumption of their bidantate involvement in metal ion coordination, most studies are muinly based on spectroscopic evidence. The (E,E)- and (£,Z)- stereoisomers of vicinal dioximes and capable of coordination through N,N"; N,0; N,Ssites of the oxime groups, and only in a few cases it is possible to realize the İntercunvention of (E,E)- and (E,Z)- complexes. The transition metal complexes of the vicinal dioximes are essentially N,N-coordinated square planar strtucturers, but the uranyl complexes from hydroxy-bridged dimers with N,0-coordinatron as shown by IR and rH-NMR. spactra. The best known example of vic-dioxime is the methyl glyoxime (H2DMG), which gives the well-known red nickel with Ni2+ far ammoniocal solution. The detailed stuructures of a fairly large of a metal vic-dioximates are known X-rey investigations. The importand features, apart from N4 planar binding, are the strong O- -H- O hydrogen binding and stacking of the planar units parallel to each other in the crystal. The number of peripheral vic-dioxime ligands reported in the literature is rather few and the heteroatoms of these substitued structurer are usually 0,N,S or binary mixtures of these donor groups. IXDepending ogon the nortive of the donor grooup, the interaction of with metal ions show different tendencies: when only and S group are present they prefer the complex with transition metal ions, while in the case in the of N and O mixtures, only partial intiraction with transition metal ions acurs with out enough interactar. In the present work, we have planned to bring together two of these donor groups (N2S2) with thw oxime moiety for the first time on the some ligand molecule. The synthetic work started with the nucleophilic in the medium of ethanol for this purpore. 2-aminothiophenol was dissolved in ethanol and treated with octyl bromide to obtain 2-octylsulfanyl amino benzene with high yield (% 73). In order to obtain the desired substitated vic-dioxime ligand, the diamino compound was reacted with cyanogen-di-N-oxide in high dilated nonpolar solvent medium. Also gradual addition oooof cyanogen-di-N-oxide which was kept -40°C provided dilute condition of two reactants to from the desired compound (oxime ligand). Novel desired transition metal oxime complexes (NiH, Co11, Fe11 and U02(II) was synthesized from the novel oxime ligand, nancly, 13,14-bis (Wdroksiimino)- 10,ll,16,17-dibenzo-9,18-ditiya-12,15-diazahegza koşan (LH2), and nitrates of metal salts. The metaMigand ratio for the [ Ni(H2L)2], [ Co(H2L)2], [ Fe(H2L)2] is 1:2 but for uranyl complexes is 2:2. the uranyl complex can be postulasted as an N,0- coordinated M-hydroxy complex of 2:2 metal: ligand ratio as encountered in the some other dioxime Ugands. while novel oxime ligand is very souble in common organic solvents, such as methanol, tetrahyrofuran, dimethylformamid the solibility of metal complexes poor in organic solvents, except in DMF, DMSO till same degree. The eluadation metal complexes have been carried out by using suitable spectral techniques, such as IR(or FTIR),1H-NMR,Mass spectra along with elemental analysis.
