Ali Cihan

Novel crown ether-substituted phthalocyanines

Abstract A novel macrocycle has been synthesized from 4′-(α-bromoacetyl)benzo-15-crown-5, 4-nitrophthalonitril and diethyl malonate; its cyclotetramerization gives Cu(II), Co(II) and Pd(II) phthalocyanines (Pcs) with four benzo-15-crown-5 substituents on the periphery. The effects of alkali metal cations with these Pcs has been investigated through the changes in the visible spectra. The newly synthesized compounds have also been characterized by elemental analyses, IR, 1 H NMR.

Synthesis and Properties of Phthalocyanines Substituted with Four Crown Ethers

Abstract New phthalocyanines substituted with four benzo-15-crown-5 units through flexible -CH2-O- chains have been synthesized from 1- {[(benzo-15-crown-5)-4′-yl]oxymethyl}-3,4-dibromo (3) or -dicyano- -benzene (4) and hydroquinone or metal salts. The crown ether group in these phthalocyanines is shown to form intermolecular sandwich type complexes with alkali metal ions leading to the aggregation of molecules.

Synthesis of New Metal-Free and Metal-Containing Phthalocyanines with Tertiaryor Quaternary Aminoethyl Substituents

Summary. A novel phthalodinitrile derivative carrying dimethylaminoethylsulfanyl groups at positions 4 and 5 was synthesized from 2-dimethylaminoethanethiol hydrochloride and 1,2-dichloro-4,5-dicyanobenzene. Its cyclotetramerization in the presence of 2-dimethylamino-ethanol or metal salts (CoCl2, Zn(OAc)2) gave metal-free or metal-containing phthalocyanines (M = Co or Zn). These phthalocyanines were converted into water soluble quaternized products by reaction with methyl iodide. The new compounds were characterized by elemental analysis, IR, NMR, and electronic spectra.

Synthesis of 4′,5′-Bis(salicylideneimino)benzo[15-crown-5] and Its Complexes with Uranyl(VI), Copper(II), Nickel(II), and Cobalt(II)

Abstract 4′,5′-Bis(salicylideneimino)benzo{15-crown-5} (SALH2) has been synthesized from 4′,5′-diaminobenzo{15-crown-5} and salicylaldehyde. The crystalline sodium nitrate complex of the ligand (SALH2.NaNO3.H2O) has also been isolated. As an N2O2-donor ligand, SALH2 forms 1:1 metal complexes with various metals {SAL(M)xH2O where M = UO2(VI), Cu(II), or Ni(II)}. The octahedral Co(II) complex of SALH2 is capable of binding molecular oxygen. Also prepared were the complexes which simultaneously contain both sodium and transition metal ion. 1H-n.m.r., i.r., u.v.-visible, and conductance data are presented.

Synthesis and characterization of novel phthalocyanines substituted with four tetraaza macrocycles

A novel copper phthalocyanine substituted with four 14-membered tetraaza macrocycles and its pentanuclear nickel(II) complex were synthesized and characterized by elemental analysis, and IR and UV spectroscopy.

Synthesis and Complexation of a Novel Soluble vic -Dioxime Ligand

Summary. A new soluble vic-dioxime 1,4-(isobutyl)-2,3-bis-(hydroxyimino)-5,6-phenylpiperazine was prepared as a mixture of isomers from anti-dichloroglyoxime and N,N′-bis-(isobutyl)-stilbendiamine which reacts to N,N′-coordinated planar metal complexes with Ni(II), Cu(II), Co(II), and Pd(II). Oxidation of the Co(II) complex in the presence of pyridine leads to an octahedral complex containing pyridine and chloride as axial ligands in addition to the vic-dioxime ligands. The uranyl complex has a 1:1 metal:ligand ratio and a dinuclear structure with μ-hydroxo bridges.

Synthesis, spectroscopy and electrochemistry of mono and dinuclear complexes of a peripherally mixed ligand and the interaction of (E, E) Ni(LH)2 with Pd2+ and Ag+

We describe the synthesis, characterization and electrochemistry of a new family of peripherally functionalised vic-dioxime, 5,6-bis-(hydroxyimino)-1,2,9,10-hydroxy-4,7-dithiadecane (LH2), with bis-(thiopropandiol) moieties attached to the oxime. Thiopolyalcohol groups containing two different heteroatoms (—S— and —O—) serve as weak exocyclic binding sites for Pd+2 and Ag+ ions. Novel mononuclear (LH)2M, (M = NiII, CuII, CoII, MnII and FeII), homodinuclear (LH)2(UO2)2(OH) and heterotrinuclear (LH)2MM′2 (M = NiII and M′ = PdII and AgI) species have been obtained with the metal:ligand ratios of 1:2, 2:2, and 3:2 respectively. Metal ions coordinate through N,N of the oxime and S,O donor sites of the peripherally attached groups in the presence of the base. The heterotrinuclear complexes were prepared by the interaction of the mononuclear complex, (LH)2Ni, with Pd(C5H5)2 and AgNO3 in an appropriate solvent. The complexes were characterized by elemental analysis, 1H-n.m.r., u.v.–vis. spectroscopy, FT-IR., and by f.a.b-m.s. The redox properties of the complexes were studied by cyclic voltammetry.

Synthesis and complexation of a novel soluble vic-dioxime with hydroxyethyl pendant arms

A new soluble vic-dioxime ligand namely 1,4-bis(2′-hydroxyethyl)-2,3-bis(hydroxyimino)-5,6-diphenylpiperazine, (LH2) containing optically active centers has been prepared as a mixture of isomers from (CNO)2 and N,N-bis(2-hydroxyethyl)stilbendiamine (1) which has been made by the reduction of the condensation of the product of benzaldehyde and 2-aminoethanol in the presence of aluminum amalgam. N,N-coordinated planar metal complexes of this ligand have been synthesized with NiII, CuII, CoII, PdII and UVIO2. Oxidation of (LH)2Co in the presence of a base, such as pyridine, leads to an octahedral complex (LH)2CopyCl containing pyridine and chloride as axial ligands in addition to vic-dioxime ligands. The structures of the ligand and its complexes are proposed on the basis of elemental analysis, 1H-n.m.r., mass, i.r. and u.v.–vis. spectral data.

Synthesis and Complexation of a Novel vic‐Dithioglyoxime

Abstract A new vic‐dioxime ligand, namely 2‐(4,5‐bishydroxyimino‐1,3‐dithiolan‐2‐ylidene)malonic acid diethyl ester (LH2), has been synthesized in two steps starting with the condensation of carbon disulphide and malonic acid diethyl ester and subsequent reaction of the dithiolate intermediate with anti‐dichloroglyoxime (DCGO) in ethanol at 5 °C. LH2 forms mononuclear N,N′‐coordinated planar metal complexes with Ni(II) and Co(II) and N,O‐coordinated (μ‐hydroxo‐bridged dimeric complex with UO2(VI). The octahedral complex (LH)2CoPyCl has been prepared by oxidation of the (LH)2Co complex in the presence of pyridine, and it has been reduced to the Co(I) derivative by NaBH4.

A New Double‐Decker Lu(III) Diphthalocyanine with Eight Peripheral Benzo(15‐crown‐5) Units

In the present study we describe a lutetium(III) bis(phthalocyaninate) complex which contains eight acetylbenzo(15‐crown‐5) units. The starting compound was diethyl (3,4‐dicyanophenyl)acetoxybenzo(15‐crown‐5)malonate (1). The synthesis of the desired compound was accomplished by the reaction of the o‐dicyano compound (1) with lutetium acetate in hexanol in the presence of 1,8‐diazabicyclo[5,4,0]undec‐7‐ene (DBU) as a strong base. The ESR spectrum confirmed the radical nature of the complex.