POLISH JOURNAL OF CHEMISTRY
Volume 74 Number 1 January 2000
Pages 1-162

1

Electrochemical Properties of Fullerene Based Solid Thin Layers

—- Winkler K., Costa D.A. and Balch A.L.

39

Ce–Ag–P System

- Demchyna R.O., Chykhrij S.I. and Kuz'ma Yu.B.

45

Preparation and Properties of Rare Earth Element 2,3-Dihydroxybenzoates

—- Kula A. and Brzyska W.

51

Synthesis of 7-Substituted 5-Dethia-5-oxacephams via [2+2]Cycloaddition of Chlorosulfonyl Isocyanate to Sugar Vinyl Ethers

—- Łysek R., Furman B., Kałuża Z. and Chmielewski M.

61

The Complexation of Protonated Amines, Diaza-18-crown-6 and Cryptand (222) by 18-Crown-6 in Different Solvents

—- Buschmann H.-J., Mutihac L., Wego A.  and Schollmeyer E.

67

Electrochemistry of Diazonium Salts. Pathways of Electrochemically Initiated Polymerization Processes

—- Koval'chuk E.P., Kozłowska Z.E., JóŸwiak L. and Błażejowski J.

79

The Kinetics of Chloromethyloxirane Reaction with Alcohols and Their Adducts in the Presence of Stannic Chloride

—- Chlebicki J. and PoŸniak R.

89

QSAR Studies on Bioorganic and Pharmacological Effects of the Antidepressants

—- Pietrzycki W.

109

Fenton Reaction of Iron Chelates Involving Polyazacyclononane. The Ligand StructureEffect

—- Szulbiński W.S.

125

Crystal and Molecular Structure of Pinane Derivatives with C₂ Symmetry. Part I. 10,10'-Biisopinocampheol

—- Karolak-Wojciechowska J. and Markowicz S.W.

131

New Compounds of Indium(III) with 2,4'-Bipyridine

—- Czakis-Sulikowska D. and Kałużna-Czaplińska J.

137

Synthesis and Crystal Structure of Tris-(1,10-phenanthroline) Nickel(II) Dichromate

- — Tang J.K., Gao E.Q., Liao D.Z., Jiang Z.H. and Yan S.P.

141

Synthesis and Properties of New 2-Alkyl-2,3,4,5-tetrahydro-1,4-benzoxazepine Derivatives. Part IV. Reduction of 2-Alkyl- 2,3,4,5-tetrahydro-1,4-benzoxazepin-3,5-diones

—- Kwiecień H. and Baumann E.

147

Synthesis and Characterization of a New Cyclobutane Substituted Schiff Base Ligand and Its Cd(II), Co(II), Ni(II) and Zn(II) Complexes

—- Cukurovali A. and Yilmaz I.

153

Neolignan Glycosides from a Cell Suspension Culture of Lactuca virosa

—- Stojakowska A. and Kisiel W.

157

Comment on the Polymorphic Forms of Metal-Free Phthalocyanine. Refinement of the Crystal Structure of a-H₂Pc at 160 K

—- Janczak J.

1-37

This paper reviews the results of investigations into the electrochemical properties of fullerenes and their derivatives in solid state. These systems can be divided into three groups: (i) polycrystalline thin layers, (ii) non-crystalline films, and (iii) fullerene based polymers. The effects of the supporting electrolyte and solvent on the electrochemical behavior of polycrystalline fullerene thin layer films are discussed. The redox properties of fullerene based self-assembled monolayers, Langmuir-Blodgett films, and fullerene incorporated bilayer lipid membranes are presented. Special emphasis is placed on the electrochemistry of fullerene based polymers. Several different methods for the electrochemical polymerization of fullerene systems are described and the properties of these systems are discussed.

39-44

Phase equilibria were established in the Ce–Ag–P ternary system up to 80 at.% of P and the CeP–CeP₂–Ag region (30–70 at.% of P) for isothermal sections at 400°C and 800°C, respectively. The isothermal sections have been formed basing on X-ray analysis. The existence of the CeAgP₂ ternary phosphide at 800°C and its decomposition to CeP, Ag₃P₁₁ and Ag, when decreasing the temperature to 400°C, has been established. Its crystal structure has been investigated using X-ray single crystal and powder methods. The CeAgP₂ compound exhibits crystal structure with tetragonal symmetry (I4/mmm space group, a = 0.4002(1) nm, c = 2.042(2) nm).

45-50

Complexes of lanthanide(III) (La–Lu) and Y(III) with 2,3-dihydroxybenzoic acid were prepared and their IR spectra, solubility in water at 293 K and thermal decomposition were investigated. When heated, the complexes with a general formula Ln(C₇H₅O₄)₃×nH₂O, where n = 0 for La–Tb, n = 4 for Dy–Tm and Y, n = 2 for Yb–Lu decompose to the oxides Ln₂O₃, CeO₂, Pr₆O₁₁ and Tb₄O₇ with intermediate formation of Ln(C₇H₅O₄)(C₇H₄O₄) (with the exception of cerium complex).

51-60

[2+2]Cycloaddition of chlorosulfonyl isocyanate (CSI) to (Z) prop-1'-enyl, (Z) and (E) 4'-trimethylsilyl-but-1'-enyl ethers of 1,2-O-isopropylidene-5-O-trityl-a-D-xylofuranose proceeds with high stereoselectivity to afford respective azetidin-2-ones. Subsequent transformations of adducts consisting in detritylation, tosylation of a terminal hydroxy group and intramolecular alkylation of the nitrogen atom give corresponding tetracyclic 5-oxacephams.

61-66

The formation of complexes between protonated amines and macrocyclic ligands is known. However, the diprotonated ligands diaza-18-crown-6 and cryptand (222) themselves are able to act as guest molecules. As a result they form complexes with 18-crown-6. The complex formation has been studied by calorimetric titrations and ¹H NMR measurements. As the macrocyclic ligands diaza-18-crown-6 and cryptand (222) contain two nitrogen atoms, they are able to form 1:1 and 2:1 complexes with 18-crown-6. The macrocyclic and macrobicyclic structure of these ammonium ions has no influence on the formation of 1:1 complexes. From the results in methanol, propylene carbonate, acetonitrile and acetone as solvents some indirect conclusions about the structure of the diprotonated ligands in solution can be drawn. The reaction between diprotonated diazacrown ethers or cryptands with crown ethers can be used for the self-assembly of larger aggregates.

67-78

The electrochemical reduction of several diazonium cations was examined on drop and stationary Hg-electrodes immersed in 1 M NaClO₄ background electrolyte and water, acetone or water–acetone mixtures. Features of ongoing processes were investigated at various reduction potentials and in the presence of acrylamide as a radical scavenger. The products of electrochemical reduction are mainly polymeric substances containing hydrogen, carbon and nitrogen. The polymerization pathways were discovered on the basis of a thorough analysis of thermochemical data obtained at the level of the semiempirical PM3 method and statistical thermodynamics. Possible applications of the electrochemical reduction of diazonium cations as polymerization (polycondensation) initiators are suggested.

79-88

Rate constants of the reaction of chloromethyloxirane (epichlorohydrin) with methyl, n-propyl, isopropyl, n-, sec-, tert-butyl, n-hexyl, n-octyl, and n-decyl alcohols in the presence of stannic chloride were studied at 30, 40, and 50°C. Reaction is not first order in respect to epichlorohydrine and is particularly fast at the beginning and its rate constants are proportional to the concentration of the catalyst. The rate constants increase in the homologous series of C₁–C₁₀ alcohols. The reaction rates of 2-chloromethyloxirane with 1-chloromethyl-2-alkoxyethanols are ca. 2.5-times larger than that with corresponding alcohols.

89-108

Quantitative Structure – Activity Relationship (QSAR) studies on 19 most important antidepressants were performed using the PM3 quantum chemical parameters. The ground state population analysis was performed for all the antidepressants (Antds), norepinephrine (NA) and serotonin (5-HT) neurotransmitters, imipramine---NA complex and  its ionic forms, asparaginate anion as active moiety in  TM III  helix of  a₁-adrenergic receptors, serine – active species in TM V helix of a₂-adrenergic receptors and  phenylalanine as actvive in TM VI  helix of  both a₁- and  a₂-adrenergic receptors of  brain frontal cortex. With the use of experimental data: K_i(j) inhibitor constants, A_j affinities and IC₅₀(j) inhibitory activities, a linear dependence of  ln 1/K_i(j), ln A_j and ln 1/IC₅₀(j) on  electronic density parameters and charge-transfer frontier orbital parameters was found. Four aspects on the biochemical and pharmacological  effects of antidepressants  are examined: (i) Blockade of  NA uptake into presynaptic nerve endings is followed by the formation of Antd---NA inactive complexes. (ii) Analogous blockade of  5-HT  uptake into presynaptic surface is accompanied by a formation of Antd---5-HT inactive complexes. (iii) Up-regulation effect of the postsynaptica₁-adrenergic receptors is followed  by high affinities of Antd---NA complexes and Antd---NA-H⁺ transition state forms for a receptor surface, accompanied by small affinities of  the antidepressants for  NA-H⁺ agonist.  (iv) Down-regulation of  the presynaptica₂-adrenergic receptors (autoreceptors) is followed by an impossibility of  formation of  Antd---NA-H⁺ ionic transition states  on  the a₂-receptor  surface.

109-124

A Fenton-like reaction of two ferrous macrocyclic complexes, one with the pentadentate ligand DPC, (DPC = N, N'-di-2-picolyl-4,7-diaza-1-oxacyclononane), and the other with the hexadentate ligand TPC, (TPC = N, N', N''-tri-2-picolyl-1,4,7-triazacyclononane) has been studied, using spectroscopic, electrochemical and kinetic analysis. Even though redox potentials of these complexes are quite similar, the rate constant of H₂O₂/[Fe²⁺DPC]²⁺ (k = 650 ± 80 M^–1 s^–1, at pH = 5.6 and 25°C) is three orders of magnitude higher than that of H₂O₂/[Fe²⁺TPC]²⁺. Because the oxidation of [Fe²⁺DPC]²⁺ ([Fe²⁺TPC]²⁺) by H₂O₂ is thermodynamically unfavourable, production of a highly reactive oxidizing intermediate, such as hydroxyl radicals (OH·) or a kinetically equivalent ferryl species ([OFe⁴⁺L]²⁺), is postulated. The resonance Raman spectrum of [Fe²⁺DPC]²⁺ treated with H₂O₂ shows a frequency at 854 cm^–1, ascribable to n(O–O) vibration modes of an iron peroxide complex with side-on geometry. The electron spin resonance spectrum of this reaction mixture, acquired at 77 K, exhibits the resonance transition, due to a low-spin Fe³⁺ complex with axial symmetry. It has been concluded that the rate of H₂O₂/[Fe²⁺TPC]²⁺ is limited by substitution of peroxide anion for one of the ligating 2-picoline. On the other hand, H₂O₂/[Fe²⁺DPC]²⁺ proceeds via rapid bonding of H₂O₂ to an open coordination site on the central cation.

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