Halit Kantekin

Synthesis and Characterization of New Metal-free and Metallophthalocyanines Substituted with Tetrathiadiazamacrobicyclic Moieties

New metal-free (5, 8) and metallophthalocyanines (6, 9) containing four diazatetrathiamacrobicycles or crosswise-disubstituted attached with two nitro and two macrobicyclic groups were synthesized by cyclotetramerization of 7,8-dicyano-4,11,22,23-tetrathia-1,14-diazapentacyclo[12.10.10.05,10.016,21.026,31]tetratriconta-5,7,12,19,20,21,28,30,32-nonane (3), 8,10-dihydro-8,11-diimino-4,14,24,34,-tetrathia-1,17-diazapentacyclo[15.13.13.05,13.019,23.028,33]tetratriconta-5,7,12,19,20,22,28,30,32-nonaisoiminoindoline (4) or 6-nitro-1,3,3-trichloroisoindolenine (7) in the presence of the corresponding metal salt or a strong organic base. The new compounds were characterized by a combination of elemental analysis and 1H NMR, 13C NMR, IR, UV–Vis and MS spectral data.

The synthesis and characterization of novel dioximes and their heteronuclear complexes containing crown ether moieties

Abstract A novel vic-dioxime S,S′-bis[2-(4′-benzylidenamino-benzo-15-crown-5)dithioglyoxime (6), with crown ether groups has been synthesized from the reaction of 4′-formylbenzo(15-crown-5) and S,S′-bis(2-aminophenyl)dithioglyoxime (4), which has been synthesized from the potassium salt of 2-aminothiophenol and dichloroglyoxime. Mononuclear complexes with a metal:ligand ratio of 1:2 have been isolated for nickel(II) and cobalt(III). The reaction of mononuclear complexes with copper(I) and cadmium(II) gives heterotrinuclear complexes. The structure of dioximes and their complexes are proposed according to elemental analyses, 1H and 13C NMR, IR, UV-vis and mass spectra.

The synthesis and characterization of new (E,E)-dioxime and its mono and heteronuclear complexes containing 14-membered tetraaza macrocyclic moiety

Abstract A new macrocyclic vicinal dioxime, 5,6:9,10:13,14-tribenzo-2,3-bis(hydroxyimino)-1,4,8,11-tetraazacyclodecane (H 2 L) has been synthesized by the reaction of ( E , E )-dichloroglyoxime with 2,3:6,7:10,11-tribenzo-1,5,8,11-tetraazadodecane ( 4 ), which was prepared by the reduction of 1,2-bis( o -nitrophenylaldimino) benzene ( 3 ). The mononuclear cobalt(III) complex ( 5 ) of the dioxime has been isolated with L′ = pyridine, together with chlorine as axial ligand. In addition, cobalt(III) complex containing the BF 2 + bridge macrocycle ( 6 ) was synthesized using a precursor hydrogen-bridged cobalt(III) complex via the template effect. The heterotrinuclear complex of the BF 2 + -capped cobalt(III) complex ( 7 ) has also been prepared by the reaction of this complex with CdCl 2 ·H 2 O. The structure of dioxime and its complexes were identified by using elemental analysis, 1 H, 13 C NMR, IR and MS spectral data.

Microwave-assisted synthesis and characterization of novel metal-free and metallophthalocyanines containing four 13-membered dithiadiaza macrocycles

Abstract Novel, tetrasubstituted metal-free phthalocyanine and metallophtalocyanines bearing four 13-membered dithiadiaza macrocycle peripheral groups were synthesized by cyclotetramerization of the phthalonitrile derivative in a multi-step reaction sequence. The new compounds were characterized by a combination of IR, 1 H NMR, 13 C NMR, UV–vis, elemental analysis and MS spectral data.

SYNTHESIS AND CHARACTERIZATION OF A NOVEL MACROCYCLIC VICDIOXIME AND SOME OF ITS MONO AND TRINUCLEAR COMPLEXES

The (E, E)-dioxime containing a dithia-dioxa-diaza macrocyclic moiety 5,6 : 11,12 : 17,18-tribenzo-2,3-bis(hydroxyimino)-1,4-diaza-7,16-dithia-10,12-dioxacyclooctadecane (H2L) has been synthesized in high yield by a 1 + 1 addition of cyanogendi-N-oxide with 2,3 : 8,9 : 14,15-tribenzo-1,16-diamino-4,13-dithia-7,10-dioxahexadecane (3) which was obtained from condensation reaction with 2-amino thiophenol and 1,2-bis(2-bromoethoxy)benzene, in dichloromethane at –10 °C. Two vic-Dioxime ligands coordinate with Ni(II), Cu(II) and Co(III) through its hydroxyimino nitrogen donor atoms by the loss of the oxime protons. Homo and heterotrinuclear CuII3 and CoIIIPdII2 complexes of this ligand have been prepared; their two ligand molecules are connected via hydroxyimino or BF2+-bridging groups and two of the metal ions are coordinated by a diaza-dithia mixed donor macrocyclic moiety. The macrocyclic ligand and its transition metal complexes have been characterized on the basis of 1H-, 13C-NMR, IR and MS spectroscopy and elemental analysis data. Synthese und Charakterisierung eines neuen vic-Dioxim-Makrocyclus und einiger seiner mono- und trinuklearen Metallkomplexe Das (E,E)-Dioxim mit dem Dithia-dioxo-diaza-Makrocyclus 5,6 : 11,12 : 17 : 18-Tribenzo-2,3-bis(hydroxyimino)-1,4-diaza-7,16-dithia-10,12-dioxacyclooctadecan (H2L) wurde in hohen Ausbeuten synthetisiert durch 1 + 1 Addition von Dicyan-di-N-oxid mit 2,3 : 8,9 : 14,15-tribenzo-1,16-diamino-4,13-dithia-7,10-dioxahexadecan (3), das durch Kondensationsreaktion von 2-Aminothiophenol und 1,2Bis(2-bromethoxy)benzol in Dichlormethan bei –10 °C erhalten wurde. Zwei vic-Dioximliganden koordinieren mit NiII, CuII bzw. CoIII uber die Hydroxoimino-Stickstoffatome unter Verlust der Oximprotonen. Homo- und heteronukleare CuII3- und CoIIIPdII2-Komplexe dieses Liganden wurden dargestellt; ihre beiden Ligandenmolekule sind uber Hydroxoimino- oder BF2+-Brucken verbunden und zwei der Metallionen werden durch die N- und S-Donoratome der makrocyclischen Einheit koordiniert. Der makrocyclische Ligand und seine Ubergangsmetallkomplexe wurden durch 1H-, 13C-NMR-, IR-, MS-Spektroskopie sowie durch Elementaranalysen charakterisiert.

Synthesis and metal ion binding properties of thiaaza crown macrocycles

Two new macrocyclic ligands (3) and (4), containing nitrogen-sulfur donor atoms, were designed and synthesized in a multi-step reaction sequence. The macrocycles (3) and (4) were used in solvent extraction of metal picrates such as Ag(+), Hg(2+), Cd(2+), Zn(2+), Cu(2+), Ni(2+), Mn(2+), Co(2+), and Pb(2+) from aqueous phase to the organic phase. The metal picrate extractions were investigated at 25+/-0.1 degrees C by using UV-visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated according to the organic solvents. The values of the extraction constants (logK(ex)) and the complex compositions were determined for the extracted complexes.

New Heavy Metal Ion‐Selective Macrocyclic Ligands with Nitrogen and Sulfur Donor Atoms and their Extractant Properties

Abstract Two new macrocyclic ligands, containing nitrogen and sulfur donor atoms were designed and synthesized in a multi‐step reaction sequence. The macrocycles with amide group were used in solvent extraction of picrates of metals such as Ag+, Hg2+, Cd2+, Zn2+, Cu2+, Ni2+, Mn2+, Co2+ and Pb2+ from aqueous phase to the organic phase. The metal picrate extractions were investigated at 25±0.1°C by using UV‐visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated according to the organic solvents. The values of the extraction constants (log Kex) and the complex compositions were determined for the extracted complexes.

Chemical Effect on K Shell X-ray Fluorescence Parameters and Radiative Auger Ratios of Co, Ni, Cu, and Zn Complexes

The production cross-sections, intensity ratios, and radiative Auger intensity ratios of Co, Ni, Cu, and Zn elements in different complexes were measured. The chemical effects on the K shell fluorescence parameters and the radiative Auger intensity ratios of these elements were investigated and the changes in these parameters were interpreted according to the charge transfer process. The samples were excited by 59.5 keV γ-rays from a 241Am annular radioactive source. K X-rays emitted by samples were counted by an Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV.

Synthesis and characterization of a novel (E,E)-dioxime and its mono- and heterotrinuclear complexes containing a 21-membered trioxadithiadiaza macrocycle

The novel (E,E)-dioxime, 5,6:17,18-dibenzo-11,12-(4-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) (H2L), has been synthesized from reaction of (E,E)-dichloroglyoxime (1) with 2,3:14,15-dibenzo 8,9-(4-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane (2). The mononuclear Co(III) complex (4) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex (5) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes (6) and (7) were prepared by reaction of (5) with NiCl2·6H2O and CdCl2·H2O, respectively. In addition, the homotrinuclear Cu(II) complex (8), has also been prepared by the reaction of this dioxime with CuCl2·H2O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1H- and 13C-NMR, IR, and mass spectral data.

Axial-ligation and macrocyclization of novel (E,E)-dioximes of nickel(II) palladium(II), platinum(II) and cobalt(III)

SummaryThe synthesis and characterization of new NiII, PdII, PtII and CoIII complexes, with the BFinf2sup+-bridged,bis(α-di-oximato) ligands are described. The initially formed six-coordinate hydrogen-bonded macrocycles, were used as metal templates to prepare the corresponding BFinf2sup+- capped macrocycles. The complexes were characterized by1H-n.m.r. and i.r. spectroscopy, and by elemental analysis.