5,6-dihidrosiklopent (f.g)asenoaftilen 1,2-diondioksim ve n,n-bis (4-benzo(15-crown-5))diaminoglioksim sentezi ve komplekslerinin incelenmesi /
Yazar: AHMET GÜL
Danışman: PROF. DR. ÖZER BEKAROĞLU
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü
Derece: Doktora, 1983
Konu: Kimya = Chemistry

Özet:
Ill II, ÖZET Yeni vic-dioksimlerin sentezi, stereoizomerlerinin ayrılması, ve oluşturdukları komplekslerin incelenmesi gurubumuz tarafından yapılan çalışmaların büyük bir bölümünü oluşturmaktadır. Diaminoglioksimin Co(II) ve Co(III) kompleksleri, bilinen vic-dioksim kemp- lekslerinden farklılıklar göstermiş ve bu kompleks lerin yapıları x-"işınları difraksiyonu ile kesin olarak belirlenmiştir, ant i ve amfi izomerleri izole edilip, farklı kompleksleri elde edilen, 1,4-difenil* 2, 3~bis(bidroksiimino)piperazin ve 1, 3-difenil^2-tiokso« 4, 5-bis( (hidroksiimino)imidazolin' in sentezi disiyan- di-N-oksit ile yapılmıştır. Çeşitli kobalt kompleks*- lerl haurlanan asenaf tilen-1, 2-diondioksim, »" mo- del bileşiği olarak dimetilglioksim kompleksleri ile karalaştırılmıştır, Ayrıca anti^monokloroglioksjm ve gnti-dikloroglioksimden çeşitli sübstitüe mono- ve diaminoglioksimler elde edilmiş ve kompleksleri incelenmiştir. Bu çalışmada önce kinon yapısındaki bir a-diketon olan 5, 6-dihidro-siklopent [f, gjasenaf tilen-1, 2 -d ion (DAD) literatürde verilenden farklı bir başlangıç maddesiyle elde edilmiş ve çözücü olarak piridin kullanmak suretiyle DAD ve hidroksilamonyum klorürden yeni bir vic-dioksim olan 5, 6-dihidrosiklopent [f, g] asenaf tiien-i, 2-diondioksim (DAOI-L) sentezi gerçek- l L leştirilmiştir, H-n.m,r. ve i.r, spektrumları PAOKk nin anti yapısında olduğunu göstermektedir. Cu(II), Ni(U), Co(II), Pd(II), Pt(II) ve Cd(II) tuzları ile DAOH^'den (DAOH)2M formülü ile gösteri-IV iebilen kompleksler elde edilmiştir. (DAOHKBXCo for mülü ile verilen oktcshedral Co(-İII) komplekslerinde ise, 1 ve 6, koordinasyonlar da, bir B komponenti (piridin, trietilamin veya tr if enilf osf in) ve bir halo~ jenür iyonu (klorür) yer almıştır. DAOH-'nin uranil iyonu ile verdiği komplekslerde metal/ligand oranı 1:1 olarak bulunmuş ve kompleksin (OH) köprüleri ile birbirine bağlanmış dimerik yapıda olduğu tesbit edil"* mistir ([(DAOH).(ÖH)U02]2). Bu çalışmanın ikinci bölümünde vic-dioksimier İn stereoizomerleri ve kompleks oluşumu üzerine taç eter lerin etkisi incelenmiştir. Bu amaçla, 4 ' -aminobenzo [ 15-crown-5 ], anti- dikloroglioksim ve aşırı miktarda NaHCO^'den mutlak etanolde N, N ' -bis(4 ! -benzo [15-crown-5 '?]> diaminoglioksim (LH~) ligandı taç eter gurupları sod yum klorür ile kompleks yapmış halde elde edilmiş ve çözeltiye NaClO. ilâvesi ile LH«« 2NaC10, hazırlanmışa tır, H-n.m.r. ve i,r. spektrumlarına göre, trans ya pıda olduğu belirlenen bu dioksimin çeşitli geçiş me~ tali kompleksleri de izole edilmiştir. (LH) ?M,4NaC104 formülü ile gösterilen kare-dilz- - ? lemsel yapıdaki Cu( 1 1 ), Ni(II) ve Co(II) kompleksle rinde metal iyonu iki diokşim moleküiündeki 4 azot atomu ile koordinasyona girmiş ve iki tane beş üyeli şelât halkası oluşturmuştur. Oktahedral Co(IÎI) komp- lerinde ayrıca eksen ligandları olarak bir B komponenti ît Benzo [15-crown-5 ]' in ÎUPAC'a göre ismi: "2,3/5,6,8,9/ll,12-oktahidro-l,4/7,10/13-benzopenta- oksasiklopentadesin"dir.(piridin veya trifenilfosf in) ve klorür iyonu yer alır. Pd(II) ve Pt(II) komplekslerinde metal iyonu oksim guruplarından birinin N atomu, diğerinin 0 atomu üze rinden koordinasyona girerek iki tane altı üyeli şelât halkası oluşturmuştur, Uranil kompleksinde dimerik bir yapı ortaya çıkmış, iki uranil iyonu iki ligand molekülü ile kompleks oluşturduktan sonra iki (OH) iyonu kompleksler arasında köprü görevi yapmışlardır. r° ® < vb HN HO Bu çalışmada sentezi gerçekleştirilen kompleks 1 lerin yapıları elemental analiz/ H-n.m^r^ i.r. ve u.v. -visible spektral verilerine göre açıklanmıştır

Abstract:
VI III, SUMMARY The synthesis and complex formation of the stereoisomers of various vic-dioximes have been the essential topics of researches carried out in this laboratory. X-ray structural analysis of Co(II) and Co(III) complexes of diaminoglyoxime has shown inter esting structures. The amphl" ana anti- stereoisomers and complexes of two new vicdioximes, namely 1,4" diphenyl-2, 3-bis(hydroxyimino)piperazine and 1,3- diphenyl-2«thioxo-4, *>-bi s (hydroxy imino) imidazoline have been isolated and interconversion of anti and qmphj complexes has been studied. Co(III) complexes of 1, 2-acenaphthylene-dionedioxime have been prepared and they are compared with dimethyglyoxime complexes as B,o model compounds, Trgnsition metal complexes of some new substituted mono- and di-aminoglyoximes have been investigated. In the first part of this work, 5t ^-dihydro- cyclopent Cf,g] acenaphthylene-1, 2-dionedioxime (DAOHo) has been synthesized from hydroxylamine hydrochloride and 5, 6-dihydrocyclopent [f,g] acenaphthylene-1, 2-dione (DAD) which has been prepared by making use of oxaly chloride as well as oxalyl bromide. In the second part, in order to increase the solubility of vic~d ioxime, crown ether groups have been added into the compound and N,N -bis(4 -benzo [15-crown-5 ] )diamjtnoglyoxime (LH«) has been synthesized. Even though the preparation of DAD through the reaction of oxalyl bromide and acenaphthene withVII aluminium chloride as the catalyst was reported earlier, later works on this subject showed that DAD could be obtained only when the catalyst was aluminium bromide. It was shown that when acenaphthene was treated with oxalyl bromide in the presence aluminium chloride di-5-acenaphthyl ketone was obtained instead of DAD. The reaction was explained by taking into consideration the decomposition of oxalyl halioes to carbon monoxide and carbonyl chloride. In this work, it is shown that oxalyl chloride can be used in DAD synthesis as well as oxalyl bromide. For this reason, it might be concluded that it is the catalyst which effects the route of the acylation reaction and not the oxaly halide which is used. DAD does not react very easily with H^NOH.HCl as some quinones such as anthraquinone; refluxing the solution of quinone and HoN0H.HCl in ethanol for days gives no dioxime, DA0Ho have been obtained when pyridine was used as the solvent. The dioxime of a symmetric a-diketone may take the anti, syn and amphi configurations. Since the syn-f orm is unable to form metal complexes, DAOHo which forms complexes with various transition metal ions should be in either anti or amphi form. A singlet at 12.10 ppm in the n.m.r. spectrum of DAOhL is strong evidence for the anti structure of the dioxime. Intra molecular hydrogen bonding in one of the oxime groups of amphi-dioxime would cause two different peaks for two oxime protons. Transition metal complexes of DA0Ho have been also isolated and their structures have been investi-VIII gqtecj by elemental analysis, i.r. and u. v. -visible spectra. It has been found that Cu( 1 1 ),Ni( II ), Co( II ), Pd( 1 1 ) f Pt ( 1 1 ) and Cd(II) form complexes with a me- tal/ligand ratio of 1:2, In the square-planar comp lexes! (Q-H.,,,0) bending vibrations are observed around 1730-171Q cm"1. Co(III) complexes of DAOrU have a B component (pyridine, triethylamine or triphenylphospine) and a chloride ion as axial Uganda other than two PAOrL molecules. These Co(III) comp lexes can be reduced to Co(I) by NapH^ in methanol/ water(3:l) without destroying the complexes. In the uranyl complex of DAOH^, a dimeric compound have been formed with two (OH) bridges between two uranyl ions* In the second part of this work, the effect of crown ether groups on the isomerism and complex forma** tion of vic-dioximes have been investigated. For this purpose,, a new vic-dioxime, LH^, has been synthesized by reaction of 4-dminobenzo- [15-crown-5] with anti- dichloroglyoxime, Since excess of NaHCO~ was added into the reaction mixture in order to neutralize HC1 formed during the reaction, NaCl came out as by-product and it complexed with the crown ether groups; therefore, the ligand was obtained as di-sodium chloride salt, LH2.2NaCl. The high stability of the alkali metal complexes of crown ethers has been confirmed during this work, since alkali metal complex did not change during the synthesis of transition metal complexes and by adding a proper anion (in this case, perchlorate) the new compounds could have been precipitated.IX In the i.r. spectrum, characteristic absorption -1 bands due to NaC10A are present at 1150-1050 cm -1 (broad band) and 640-430 cm (doublet) both in LHo^NaClO^, and in the complexes which contain NaClO^o The structure of LH«.2NaX has been determined to be in trans form as diaminoglyoxime. In the i.r, spectra of LH9.2NaX, v(0H) vibration is observed at -1 3260 cm as a broad absorption. v(C=N), 6(0~M), and -1 v(N-O) bands are at 1640,1425 and 945 cm, respectively* these values are in harmony with the previously reported diaminoglyoxime derivatives. In the H-n,m.r<, spectrum of LH2. 2NaC104/ the chemical shifts for OH and NH protons are observed at 10,2 and 8,2 ppm, respectively. Other than these two bands which disappear on deuterium exchange, two multiplets at 3,7-3.4 and 6.9-6.3 ppm correspond to etheral (CH^-CH^-O) and aromatic protons. As in the cases of most anti-dioximes, LH« forms complexes with Cu(II), Co(II) and Ni(II) with a metal/ ligand ratio of 1:2. The i.r. spectra of these comp lexes exhibit v(C=N) absorptions between 1610-1570cm which is lower than the value for the free ligand (1640 cm ). This suggest that LH ligand is N,N coordinated to Cu(II), Co(II) and Ni(II). As expected o for d-conf iguration in square-planar field, Ni(II) complex is diamagnetic according to the n.m.r. spectrum. In the H-n.m.r. spectrum of Ni(II) complex, NH proton has been observed at 7.9 ppm and intramolecular H- bridged OH protons have been shifted to 16.2 ppm. Octahedral Co(III) complexes of LH«.2NaCl are prepared as those of dimethylglyoxime, DA0H?/ and 1, 2-atenaphthyl- enediondioxime. Pyridine or tr iphenylphosphine is usedX as axial ligqnd in (LH) 2BClCo,4NaClQ4, (LH)2Pd,4NaC104 and (!_H)2Pt.4NaC104 compiles are prepared in a similar way from PdCl« and PtCI* in ethanol. NaCl was used to dissolve these two chloridesas Na^PdCl. and Na^PtCl.. Since Na«PtCl4 is not stable in ethanol, LH~. 2NaCl is added simultaneously wit the metal salt. Even though they have the same metal-ligand ratio, LH?.2NaX complexes of Pd(II) and Pt(II) are coordinated in a different way than Cu(II)^ Ni(II), and Co(II). In the 1H-n.m.r. spectra of Pd(II) and Pt(II) complexes, even though NH protons are not effected from complex formation, the OH signals have been shifted to 9,2 ppm and the integral curve showed 1:2 ratio for OH : NH. Since the formation of 0-H...0 bands results a shift to the lower field, the ligand should from a six-membered chelate ring by coordinating to Pd or Pt through N and 0 atoms. This type of coordi nation is more usual in amphi-dioximes and in the Ni(II) complex of a-camphorquinonedioxime the uncoordinated OH protons show a chemical shift of 0,5 ppm to the higher field. The weakening of the 6(OH) band at 1425cm and the appearence of another v(C=N) vibration at 1570 cm also confirm the proposed structure, [(LH) (OH) U0«] *.4NaX complexes were prepared from both LH2.2NaCl and LH2.2NaC104. It is slighly soluble in ethanol even in the case of NaCl salt. The uranyl complex can be precipitated also in water when excess of sodium perchlorate has been added into the solution, H-n.m.r. spectra of the uranyl complexes show two peaks for N-OH protons(10.7 and 10.3 ppm) and two peaks for NH protons (8.3 and 7.9 ppm). The ratio of N0H:NHXI in the integral curve is 1:2. There is also another D«0 exchange able shift at 4,1 ppm(2H) which can be assigned to hydroxy 1 groups coordinated to uranyl ions. It is known that the uranyjl ion enhances the chemical shift difference between the non- equivalent protons. This effect is equivalant to increasing the H-nmr, observing frequency by a few orders of magnitude. The magnetic anisotropy of the uranyl ion has also been discussed in relation to some carboxy late and amine complexes. Therefore, the H-n.m.r# data enable» us to propose a hydroxy-bridged uranyl(VI) dimer similar to [(N03)2UO2(OH)2UO2(H2O)3].H2O. The i. r. spectrum is also consistent with the dimeric -1 ? structure. A strong band around 905 cm is the characteristic frequency for v(0=U=0) vibrations. The electronic spectrum shows a strong absorption at 410 nm which is assigned to charge transfer transition from the pn orbital of the donor atoms to 5f and 6d orbitals of uranium. Elemental analysis results also confim the dimeric complex, The extra ordinary solubility of the complexes of H2L.2NaX in water and in most of the other common solvents especially when NaCl is the salt complexed in the crown ether moiety should be mentioned.