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YENİ KARBONİL-OKSIM LIGANTLARININ ve BAZI GEÇİŞ METAL KOMPLEKSLERİNİN SENTEZLENEREK YAPILARININ AYDINLATILMASI ÖZET Bu çalışmada; oksim grubuna komşu durumda hem C=0, hem de -NH-R grubu bulunduran 4 adet tek oksim grubuna sahip ve 1 adet iki oksim grubu içeren toplam 5 adet karbonil oksim ligantı ve bu ligantların geçiş metal katyonlarından Co(II), Ni(II), Cu(II) ile oluşturdukları kompleksleri sentezlendi. Ligantların kimyasal yapıları elementel analiz, İR, UV-Vis., 'H-NMR spektral verileri ve X-ışınları tek kristal yapı analizi teknikleri ile karakterize edildi. Komplekslerin kimyasal yapıları; elementel analiz, İR, UV-Vis., manyetik moment ölçümü, termik analiz teknikleri ile belirlendi. Bir tane oksim grubu içeren ligantların metal iyonuna oksim azotu, oksim oksijeni ve amid azotundan bağlanarak dimerik veya polimerik yapıda kompleksler oluşturdukları ve komplekslerinin antiferromanyetik özellik gösterdikleri belirlendi. İki oksim gurubu bulunduran ligantm metal iyonuna oksim azotu, oksim oksijeni, amid azotundan ve karbonil gruplarından biri ile bağlanarak trimerik yapıda kompleksler oluşturdukları gözlendi. Termik analiz çalışmaları ile komplekslerin içerdiği suyun metal iyonuna koordine olmadığı ve komplekslerin termik bozunması sonucu metal oksitlerin kaldığı belirlendi. Metal-ligant oranı L1_4H2 ligantlarmm Ni(II) ve Cu(II) komplekslerinde 1:1, L!H2 ligantının Co(II) kompleksinde 1:1, L2`4H2 ligantlannın Co(II) komplekslerinde 2:3 olarak belirlendi. L5H4 ligantının ise metal-ligant oranı 3:2 olan trinükleer kompleksler oluşturdukları önerildi. L1_4H2 ligantının nikel, bakır ve kobalt kompleksleri için tetrahedral yapı önerildi. Anahtar Kelimeler: Oksim, karbonil oksim, amid oksim, dion monoksim 11 THE SYNTHESIS AND CHARACTERIZATION OF NEW CARBONYL- OXIME LIGANDS AND THEIR COMPLEXES WITH SOME TRANSITION METALS ABSTRACT In this work, newly synthesised five carbonyl-oxime ligands were studied. The ligands consist of a C=0 group and an -NH-R group adjacent to the oxime group. Four ligands have one oxime functional group, whereas one ligand has two oxime groups. The ligands were characterized by elemental analysis, IR, UV-Vis., ^-NMR and single crystal X-Ray difractometry techniques. The Ni(II), Cu(II) and Co(II) complexes of these ligands were synthesized and defined by means of elemental analysis, IR, UV- Vis. Spectroscopic methods, magnetic measurements and thermal analysis techniques. The ligands containing one oxime group as negatively charged (-2) ligands were found to coordinated to the metal ions via the oxime nitrogen, oxime oxygen and amide nitrogen atoms. A polymeric structure was suggested for the complexes. The complexes showed antiferromagnetic effect. The ligand which containing two oxime groups as a negatively charged (-3) ligands coordinated to the metal ions through the oxime nitrogen, oxime oxygen, amide nitrogen atoms and the oxygen atom of the carbonyl group. A trimeric structure was suggested for the complexes of the ligand. Based on thermal analyses data, the water in the complexes was found to be non- coordinated to the metal ions. Metal-ligand ratio was found to be 1:1 for the Ni(II) and Cu(II) complexes of L1` 4Ü2 ligands. In the Co(II) complexes this ratio was found to be 2:3 except Co(II) complexes of L1!^ ligand. The complexes of L14H2 ligands were assumed to match to polymeric form. In the complexes of L5H4, the metal-ligand ratio was determined to be 3:2 and complexes formed in trimeric structure. The tetrahedral structures were suitable for the Co(II), Ni(II) and Cu(II) complexes of L1` H2 ligands. Keywords: Oxime, carbonyl oxime, amid oxime, dion monoxime 141

ÖZET Oksim ligandlan yapılarında `-C-NOH` fonksiyonel grubu bulunduran, geçiş metalleri ile katı, kararlı kompleksler oluşturan organik maddelerdir. Oksimler kararlı olmalarına rağmen uzun süre ısı ve ışık etkisinde kalırlarsa bozunurlar, Oksimlerin geçiş metalleri ile oluşturdukları komplekslerin çözünürlükleri genellikle düşüktür. Bu çalışmada; hidroksilaminhidroklorür ile kloralhidrattan anti-kloroglioksim ve anti-dikloroglioksim sentezlenerek yeni sübstitüe aminoglioksimlerin sentezinde kullanıldı. Ar-NH2 ve Ar-SH tipindeki bileşikler anti-kloroglioksim ve anti-dikloroglioksim ile -5 °C ve altındaki sıcaklıklarda etkileşerek simetrik ve simetrik olmayan glioksimleri oluştururlar. 3,4-dimetilaniIin ve 3,4-dikloranilin ile anti-kloroglioksim kullanılarak simetrik olmayan N-(3,4-dimetilfenil)aminoglioksim ve N-(3,4- diklorofenil)aminoglioksim ligandı, anti-dikloroglioksim kullanılarak simetrik olan N-N'- bis(3,4-dimetilfenil)diaminoglioksim ve N,N'-bis(3,4-diklorfenil)diaminoglioksim ligandı sentezlendi. Sentezlenen bu ligandların alkoldeki çözeltisine metal-ligand oranı 1:2 olacak şekilde NiCl2.6H20, CuCI2.6H20 ve CoCl2.6H20' nun alkoldeki çözeltileri ilave edilip 40-50 °C'de pH'ı 4-5 civarına ayarlanarak kompleksler sentezlendi. Saflaştırılan komplekslerin ve ligandların yapıları UV-VİS, İR, 'H-NIVIR, manyetik duyarlık ve elementel analiz yardımıyla aydınlatıldı. Nikel ve bakır komplekslerinin kare düzlem, kobalt komplekslerinin ise oktahedral yapıda oldukları tesbit edildi. Anahtar Kelimeler: N-(3,4-dimetilfenil)aminoglioksim N-(3,4-diklorofenil)aminoglioksimdiklorglioksim N-N'-bis(3,4-dimetüfenil)diaminoglioksim N,N'-bis(3,4-diklorfenil)diaminoglioksim Oksimler. ABSTRACT Oxime ligands have `-ONOI I` functional group in structure and can form stable complexes with transition metals. Although the complexes very stable they can be decomposed after prolonged exposition to light or high temperature. Solubility of the complexes are generally low. In this study anti-chloroglyoxime and anti-dichloroglyoxime were synthesised using hydroxylaminehydrochloride and chlorahydrate and these were used to prepare corresponding new aminoglyoximes. Compounds such as Ar-NH2 and Ar-SH react with anti-chloroglyoxime and anti- dichloroglyoxime at -5 `C and below this temperature, forms symmetrical and unsymmetrical glyoximes. 3,4-dimethylaniline, 3,4-dichloroaniline and anti- chloroglyoxime were used to prepare unsymmetrical N-(3,4- dimethylphenyl)aminoglyoxime, N-(3,4-dichlorophenyl)aminoglyoxime. The substituted anilines and anti-dichloroglyoxime were used to prepare corresponding symmetrical diaminoglyoximes. The complexes were prepared by mixing solution of the NİCI2.6H2O, CuCİ2.6H20, C0CI2.6H2O in alcohol with certain a amount of solution of the ligands in alcohol to maintain transition metal-ligand ratio 1:2 at 40-50 `C in the pH rage 4-5. The structure and physical properties of the purified complexes and ligands were determined by UV-VIS, IR, 'H-NIvIR spectra, magnetic susseptibity and elemental analysis. The structure of the Nickel and Copper complex were found to be square-planar while Cobalt complexes were octahedral. Key Words: N-(3,4-dimethylphenyl)aminoglyoxime N-(3,4-dichlorophenyl)aminoglyoxime N-N'-bis(3,4-dimethylphenyl)diaminoglyoxime N-N'-bis(3,4-dichlorophenyl)diaminoglyoxime Oximes 61

YESILEL, Okan Zafer/0000-0002-2284-1578 WOS: 000340315200044 Two new cyano-bridged two-dimensional heteronuclear complexes, [Cd(NH3)(2)(mu-ampy)Ni(mu-CN)(2)(CN)(2)](n) (1) and [Cd(H2O)(2)(mu-amPY)Pt(mu-CN)(2)(CN)(2)](n) (2) (ampy = 4-aminomethylpyridine), were synthesized and characterized by FT-IR and Raman spectroscopic, thermal (TG, DTG and DTA) and elemental analyses and single crystal X-ray diffraction techniques. They crystallize in the triclinic system and P-1 space group. The Ni(II) or Pt(II) ions are four coordinate with four cyanide-carbon atoms in a square planar geometry and the Cd(II) ion exhibits a distorted octahedral coordination by two different N-atoms from two symmetrically equivalent ampy ligands, two ammine or aqua ligands and two bridging cyano groups.The most important features of the complexes are the presence of obvious M center dot center dot center dot pi (M = Ni(II) or Pt(II)) interactions. (C) 2014 Elsevier B.V. All rights reserved. Eskisehir Osmangazi UniversityEskisehir Osmangazi University [201219A202] This work was supported by the Research Fund of Eskisehir Osmangazi University. Project number: 201219A202. Raman spectra were recorded at Anadolu University, Department of Physics. The authors wish to thank Prof. Dr. Mustafa Senyel and Mrs. Tulay Tiras for the Raman measurements.

Bu çalışmada ikincil ligant olarak imidazol ve türevlerini içeren ligantlar kullanılarak [imidazol (imd), 2-metilimidazol (2Mimd), 2-etil-4-metilimdazol (2E4Mimd), N-metilimidazol (NMimd) ve 2-isopropilimidazol (2IPimd)] karışık ligantlı beş tane Cd(II)-p-aminosalisilat kompleksi mikrodalga sentez yöntemi kullanılarak sentezlenmiştir. Komplekslerin yapıları, IR spektroskopisi ve X-ışınları kırınım yöntemi ile aydınlatılmış ve termik özellikleri belirlenmiştir.Yapılan çalışmalar sonucunda p-aminosalisilat ligantının (PAS) karboksil grubundaki hidrojenin ayrılması ile monoanyonik olarak 1 kompleksinde çift dişli ve tek dişli; 2, 4 ve 5 komplekslerinde çift dişli, 3 kompleksinde ise tek dişli olarak Cd(II) iyonuna koordine olduğu; 2 ve 5 komplekslerinin mononükleer diğerlerinin polimerik yapılı olduğu tespit edildi.Komplekslerin kapalı formüllerinin 1 için {[Cd2(PAS)4(imd)2]?4H2O}n; 2 için [Cd(PAS)2(2Mimd)2]; 3 için {[Cd(PAS)2(2E4Mimd)]?H2O}n; 4 için {[Cd(PAS)?(NMimd)?]}n; 5 için [Cd(PAS)?(2IPimd)2] şeklinde olduğu belirlendi.Termik analiz çalışmaları, komplekslerin susuz hallerinin bozunmalarında ilk önce imidazol veya türevlerinin yapıdan ayrıldıklarını veya bozunduklarını, daha sonra ise PAS ligantlarının ekzotermik olarak yapıdan ayrıldıklarını göstermektedir.Susuz hallerinin ilk bozunma basamaklarının DTAmax. sıcaklıkları dikkate alındığında bileşiklerin termik kararlılık sırası;İmidazol > 2-metilimidazol > N-metilimidazol > 2-etil-4-metilimidazol > 2-isopropilimidazolşeklinde belirlendi. In this work, novel five mixed ligand Cd(II)-4-aminosalycilato complexes which are containing imidazole and its some derivatives [imidazole (imd), 2-methylimidazole (2Mimd), 2-ethyl-4- methylimidazole (2E4Mimd), N- methylimidazole (NMimd) and 2-isopropylimidazole (2IPimd)] as secondary ligand, were synthesized by using microwave radiation.The structure of the complexes were characterized by using IR spectroscopy and X-Ray single crystal diffractions methods and also the thermal behavior of the complexes were investigated.The p-aminosalicylic acid (PAS) acted as monoanionic ligand by separating of hydrogen in carboxyl group in all complexes. It were found; the p-aminosalicylic acid (PAS) acted as mono and bidentate in manner for complex 1, bidentate in manner for compounds 2, 4 and 5 and monodentate in manner for complex 3. The compound 2 and 5 was found as in mononuclear and the others were found as in polymeric form. The formular of the compounds found as {[Cd2(PAS)4(imd)2]?4H2O}n, [Cd(PAS)2(2Mimd)2], {[Cd(PAS)2(2E4Mimd)]?H2O}n, {[Cd(PAS)?(NMimd)?]}n and [Cd(PAS)?(2IPimd)2] for 1, 2 ,3 ,4 and 5, respectively.The thermal analyses works showed that in the first step, the imidazole or its derivatives was removed in the anhydrous form of the complexes and then the PAS ligands were exothermically removed from the compound.In the consideration of the anhydrous form of the complexes, the thermal stabilities of the compounds was determined asimidazole > 2-methylimidazole > 2-ethyl-4- methylimidazole > N- methylimidazole > 2-isopropylimidazole 88

Bu çalışma ile tiyofen-2-karboksilik asitin (HTCA), imidazol (im) ligantı içeren kompleksleri sentezlenmiş, yapıları X-ışınları tek kristal kırınım yöntemi ile aydınlatılmış, spektroskopik (IR ve UV-Gör.), manyetik ve termal özellikleri incelenmiştir.Komplekslerde tiyofen-2-karboksilik asitin monoanyonik formda tek dişli olarak metal iyonuna karboksilik asit oksijeninden bağlandığı, imidazol ligantının ise azot atomu üzerinden metal iyonlarına koordine olduğu belirlenmiştir. Komplekslerin kapalı formüllerinin mangan, kobalt ve kadmiyum kompleksleri için [M(TCA)2(H2O)2(im)2], bakır kompleksi için ise [Cu(TCA)2(im)2] şeklinde olduğu belirlenmiştir. Mangan, kobalt ve kadmiyum komplekslerinin [MO4N2] tipinde oktahedral geometrili, bakır kompleksinin ise [CuO2N2] tipinde karedüzlem geometrili olduğu bulunmuştur. Manyetik moment ölçümleri ile komplekslerin zayıf alan kompleksleri oldukları bulunmuştur.Komplekslerin susuz hallerinin ilk bozunma basamaklarına ait DTGmaks. sıcaklıkları dikkate alındığında termik kararlılık sırasının Co (273°C)>Cu (229°C)>Cd (175°C)>Mn (167°C) şeklinde olduğu belirlenmiştir. In this study, the complexes containing thiophene-2-carboxylic acid (HTCA) and imidazole (im) ligants were synthesized and characterized by X-ray single crystal diffraction method. Also, spectroscopic (IR and UV-Vis.), magnetic and thermal properties were investigated.In the complexes, the thiophene-2-carboxylic acid acted as monoanionic monodentate manner and bonded to the metals via its carboxylate oxygen. The imidazole ligants bonded to the metals via its nitrogen atoms.The formula of the complexes were found as [M(TCA)2(H2O)2(im)2] (M: Mn, Co, Cd) and [Cu(TCA)2(im)2].The geometry around the metal centers were found as octahedral [MO4N2] type for manganese, cobalt and cadmium complexes and found as square-planar [CuO2N2] type for copper complex. Magnetic susceptibility measurements showed the complexes were in low ligant field complexes.In the consideration of anhydrous form of the complexes, the thermal stability of the complexes was suggested as Co (273°C)>Cu (229°C)>Cd (175°C)>Mn (167°C). 89

WOS: 000319325600022, Tetra[N-phenylanthranilato](O,O)bis[2-amino-4-methyl) pyridine copper(II)] (bisdichloromethane solvate and unsolvate) in one crystalline contains two independent binuclears, one of which is unsolvate and the other one is dichloromethane solvate. The phenyl ring planes in the asymmetric units were not parallel to each other [44.47(14)degrees and 52.50(13)degrees for unsolvate unit, 53.30(14)degrees and 49.59(13)degrees for solvate unit] and the distance between the two centers of phenyl rings was measured as 5.064 angstrom (for Cg2-Cg3), 5.005 angstrom (for Cg4-Cg5), 5.048 angstrom (for Cg7-Cg8), and 5.088 angstrom (for Cg9-Cg10) for NPA ligands. The complex molecules showed three dimensional supramolecular networks by OH center dot center dot center dot O, CH center dot center dot center dot O, CH center dot center dot center dot, and center dot center dot center dot interactions.

WOS: 000313928000005, The two complexes of Bis(4-aminosalicylato-O) bis(N,N-dimethylethylenediamine)Ni(II) with different colors, were synthesized by the reaction between sodium salt of 4-aminosalicylic acid (PAS-Na), Ni(NO3)(2) center dot 6H(2)O and N,N-dimethylethylenediamine in the ethanol water mixture. In the complexes, each Ni(II) atom was in a distorted octahedral environment, was coordinated apically by two 4-aminosalicylato-O atoms and equatorially by two the N,N-dimethylethylenediamine N atoms. The crystal structures (monoclinic, P21/n space group) of the complexes, comprise mononuclear {Ni(NH2OHC6H3COO)(2) center dot [NH2CH2CH2N(CH3)(2)](2)} species and the Ni(II) atoms were located on a crystallographic inversion centre. The bond lengths and bond angles were nearly same with showing small difference as approximately 1% in coordination bonds lengths which caused the different colors for complexes. The N-H center dot center dot center dot O, C-H center dot center dot center dot O and C-H center dot center dot center dot pi inter-molecular interactions, extended the molecules through the three axes to form three dimensional network.

TAS, MURAT/0000-0002-2879-6501; WOS: 000287712400027 The complexes were synthesized by the reaction between sodium salt of p-aminosalicylic acid (PAS) and Cu(II) for 1 and corresponding ethylenediamine (en) or its derivatives for 2-6. The complexes were characterized by using elemental analyses, FT-IR, UV-Vis, magnetic moment measurements, and thermal analyses techniques. In complex 1[Cu-2(PA)(4)(H2O)(2)], two Cu(II) ions were found as bridged by four mu-O:O' p-aminosalicylato (PA) ligands, forming a cage structure, and two aqua ligands to form dinuclear square-pyramidal geometry around Cu(II) ions. In the complexes 2-6, the PA (anionic form of p-aminosalicylic acid) coordinated to Cu(II) ions as monodentate manner by using its oxygen atom of deprotonated carboxylic acid and ethylenediamine derivatives coordinated to the Cu(II) ions in bidentate manner to form mononuclear octahedral complexes [Cu(PA)(2)(L)(2)] (L = ethylendiamine, N,N-dimethylethylendiamine, N,N'-dimethylethylendiamine, N,N,N',N'-tetramethylethylendiamine, and 1,3-propanediamine, for complexes 2, 3, 4, 5, and 6, respectively). In all the complexes OH and NH2 groups of PA ligands were not coordinated to metals.