POLISH JOURNAL OF CHEMISTRY
Volume 73 Number 9 September 1999
Pages 1437-1593


CONTENTS


REVIEW ARTICLE


1437-1450

Zirconium Species as Tools in Phosphorous Chemistry

— Zabłocka M., Skowrońska A., Igau A. and Majoral J.-P.


INORGANIC CHEMISTRY


1451-1456

Synthesis and Magnetism of Nickel(II) Binuclear Complexes with Oxamide-N,N'-diacetic Acid

— Han K.Q., Tian Z.Q., Wei K.J., Ma S.L., Lu L.L., Meng X.F., Yang X.L., He M. and Gao J.


1457-1463

Synthesis of 9,10-Bis(hydroxyimino)-4,8,11,15-tetraaza-1,2,17,18-O-dicyclopentylideneocta- decane and Its Complexes with Co(II), Co(III), Cu(II) and Ni(II)

— Çukorovali A. and Tas E.


1465-1471

Interactions Between the Components in the Ti–Cu–Sn System at 670 K

— Koblyuk N.O., Akselrud L.G. and Skolozdra R.V.


ORGANIC CHEMISTRY


1473-1475

Synthesis of O,O,O-Triaryl Phosphorothioates and O-Aryl Phosphorodichloridothioates Using Poly(ethylene glycol) as a Phase Transfer Catalyst

— Jadhav V.K., Wadgaonkar P.P. and Salunkhe M.M.


1477-1487

3'-Alkylsulfinyl-4-alkylthio and 3',4-Di(alkylsulfinyl)-3,4'-diquinolinyl Sulfides

— Maślankiewicz M.J.


1489-1502

The Influence of Cations Complexed by Crown Ethers on Anthracene Charge-Transfer Interactions

— Ostaszewski R. and KoŸbiał M.


PHYSICAL CHEMISTRY


1503-1511

Liquid Crystalline Properties of Azobenzenes: II. 4-Pentyloxy-, 4-Hexyloxy- and 4-Heptyloxy-4'-alkyloxyazobenzenes

— Galewski Z.


1513-1522

Kinetics of the Hydrogen Chloride/Methanol-Catalyzed Mutarotation Reaction of N-(p-Chlorophenyl-b-D-glucopyranosylamine)

— Smiataczowa K.


1523-1534

Electrochemical Studies of Trilayers of Conducting Polymers

— Żabczyńska K. and Maksymiuk K.


1535-1548

Acid Properties of HY Zeolite Dealuminated by Steaming and EDTA Treatment – NMR, XPS and IR Studies

— Datka J., Gil B., Złamaniec J., Batamack P., Fraissard J. and Massiani P.


1549-1554

A post Hartree-Fock Quantum-Chemical Study of the Dimerization of 2-Pyrrolidinone

— Gorb L., Jadżyn J. and Wojciechowski K.W.


1555-1562

Effects on the Micellar Solubilization of Organic Compounds by Surfactant Micelles.
II. Nature and Position of Substituent Groups in Aromatic Acids

— Higazy W.S. and Mahmoud F.Z.


1563-1579

Predictions of Mixed-Gas Adsorption Equilibria from Pure Component Adsorption Data:
A Comparative Study of the Integral Equation Approaches

— Nieszporek K.


COMMUNICATIONS


1581-1586

Crystal and Molecular Structure of 2-{o-Phenylene-[1-(o-phenyleneamino)ethyl]imino}-4-methylquinoline

— Karczmarzyk Z., Kopeć T. and Lewiński J.


1587-1592

Synthesis and Structure of Diiodo(phthalocyaninato(2-))tin(IV)

— Janczak J. and Kubiak R.










Zirconium Species as Tools in
Phosphorous Chemistry

by M. Zablocka1, A. Skowronska1, A. Igau2 and J.-P. Majoral2*

1Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
90-363 £ódŸ, Sienkiewicza 112, Poland
2Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne,
31077 Toulouse, Cedex, France

(Received March 22nd, 1999; revised manuscript May 10th, 1999)

Interactions between different zirconium compounds as Schwartz reagent [Cp2ZrHCl]n, zirconocene [Cp2Zr] or benzyne zirconocene and unsaturated systems incorporating main group elements have been investigated. Efficient new methodologies of preparation of several linear mono-, di-, tri- or polyphosphanes as well as mono-, di- or tricyclic compounds incorporating phosphorus, nitrogen, antimony or tin are reported.





Synthesis and Magnetism of Nickel(II) Binuclear Complexes with Oxamide-N,N'-diacetic Acid

by K.Q. Han, Z.Q. Tian, K.J. Wei, S.L. Ma, L.L. Lu,
X.F. Meng, X.L. Yang, M. He and J. Gao

Department of Food Engineering, Tianjin University of Commerce, Tianjin 300400, P. R. of China

(Received March 2nd, 1999; revised manuscript April 29th, 1999)

Three novel m-oxamidato binuclear complexes have been synthesized, namely [Ni(oxaa)Ni(L)2(H2O)2]×xH2O, where oxaa is oxamide-N,N¢-diacetic acid tetraanion and L denotes 2,2¢-bipyridyl (bpy), 4,4¢-dimethyl-2,2¢-bipyridyl (Me2bpy) or 1,10-phenanthroline (phen). The temperature dependences of the magnetic susceptibilities of [Ni(oxaa)Ni(bpy)2(H2O)2] and [Ni(oxaa)Ni(phen)2(H2O)2]·H2O have been investigated in the 4.2–300 K range, giving the exchange parameters J = –25.3 cm–1 for bpy and J = –26.4 cm–1 for phen, respectively. These results are commensurate with antiferromagnetic interaction between the adjacent metal ions.





Synthesis of 9,10-Bis(hydroxyimino)-4,8,11,15-tetraaza-1,2,17,18-O-dicyclopentylideneoctadecane
and Its Complexes with Co(II), Co(III), Cu(II) and Ni(II)

by A. Çukurovall and E. Taº

F1rat University, Faculty of Arts and Sciences, Chemistry Department, 23119 Elaz1g, Turkey

(Received March 23rd, 1999; revised manuscript May 14th, 1999)

A novel dioxime 9,10-bis(hydroxyimino)-4,8,11,15-tetraaza-1,2,17,18-O-dicyclopentylideneoctadecane (LH2) was prepared by the reaction of 1,2-O-dicyclopentylidene-4-aza-7-aminoheptane and (E,E) dichloroglyoxime in THF. Mononuclear complexes with a metal-ligand ratio of 1:2 were prepared with Co(II), Cu(II) and Ni(II). An octahedral Co(III) complex of the ligand was prepared with pyridine (py) and chloride ion as axial ligands. The authenticity of the ligand and its complexes was established by elemental analyses, IR, 1H and 13C NMR spectra, magnetic susceptibility measurements, thermogravimetric analyses (TGA) and differential thermal analyses (DTA).





Interactions Between the Components in the
Ti–Cu–Sn System at 670 K

by N.O. Koblyuk, L.G. Akselrud and R.V. Skolozdra

Inorganic Chemistry Department, Ivan Franko Lviv State University,
Kyryla and Mefodiy 6, 290005 Lviv, Ukraine
E-mail (to N.O.Koblyuk): kobl@chem.franko.lviv.ua

(Received January 18th, 1999; revised manuscript May 17th, 1999)

The isothermal section of the phase diagram of the Ti–Cu–Sn system has been constructed at 670 K and phase equilibria at this temperature  were determined. A new TiCuSn ternary compound was obtained and its crystal structure was studied. This  compound crystallizes in the LiGaGe structure type (space group P63mc, a = 4.3972(1) Å, c = 6.0168(2) Å, which is a superstructure of the CaIn2 type. Reported early TiCu2Sn has a homogeneity range – Ti1–xCu2+xSn (x = 0.0–0.3). Electrical resistivity of TiCuSn has been measured,   exhibiting  metallic conductivity.





Synthesis of O,O,O-Triaryl Phosphorothioates and O-Aryl Phosphorodichloridothioates Using Poly(ethylene glycol) as a Phase Transfer Catalyst

by V.K. Jadhav1, P.P. Wadgaonkar2 and M.M. Salunkhe1

1Department of Chemistry, The Institute of Science, 15, Madam Cama Road, Mumbai-400 032, India
2Polymer Chemistry Division, National Chemical Laboratory, Pune-411 008, India

(Received December 21st, 1998; revised manuscript April 23rd, 1999)

O,O,O-Triaryl phosphorothioates and O-aryl phosphorodichloridothioates have been prepared in good yields and purity from thiophosphoryl chloride and phenol using poly(ethylene glycol)-400 (PEG-400) as a phase transfer catalyst.





3'-Alkylsulfinyl-4-alkylthio and 3',4-Di(alkylsulfinyl)-3,4'-diquinolinyl Sulfides

by M.J. Maślankiewicz

Institute of Chemistry, Silesian University, Szkolna Str. 9, 40-006 Katowice, Poland

(Received January 29th, 1999; revised manuscript May 5th, 1999)

Reaction of 3¢,4-di(alkylthio)-3,4¢-diquinolinyl sulfides 1 with nitrating mixture started with 3¢-methylthio group monooxidation and yielded the 3¢-alkylsulfinyl diquinolinyl sulfides 2 as the primary products. Further treatment of 2 with nitrating mixture proceeded as 4-alkylthio group oxidation to give the mixture of disulfoxides 3 and 4, which underwent hydrolysis (in 90% sulfuric acid) to 3¢-alkylsulfinyl-4(1H)-quinolinones 5.





The Influence of Cations Complexed by Crown Ethers on Anthracene Charge-Transfer Interactions

by R. Ostaszewski1* and M. KoŸbiał2

1Institute of Organic Chemistry, Polish Academy of Sciences, 01-224, Warsaw, Kasprzaka 44/52, Poland
2Institute of Physical Chemistry, Polish Academy of Sciences, 01-224, Warsaw, Kasprzaka 44/52, Poland

(Received April 20th, 1999; revised manuscript May 10th, 1999)

Formation of organic charge-transfer complexes of two anthracene derivatives with tetracyanoethylene (TCNE) was monitored by spectroscopic methods. Both compounds form complexes with TCNE, which are exothermic and enthalpy driven.  For compound 3 and TCNE, the association constant is K = 395 M–1.  The presence of crown ether rings in compound 5 diminishes the association constant to K = 290 M–1.  Additional complexation of potassium cation decreases the charge-transfer (CT) association to K = 142 M–1. This effect is not influenced by the second potassium cation. It is evident from NMR data that TCNE acceptor molecule is rocking over anthracene and incorporation of crown ether rings into anthracene structure slows down the kinetics of formation of the CT complex.  Additional complexation of potassium cation by crown ether rings present in anthracene 5 causes a further decrease of the complexation kinetics. The overlap of donor and acceptor molecules according to X-ray data was complemented by the observation that the kinetics of complex formation is strongly dependent on the substituent present in the donor anthracene molecule.





Liquid Crystalline Properties of Azobenzenes:
II. 4-Pentyloxy-, 4-Hexyloxy-
and 4-Heptyloxy-4'-alkyloxyazobenzenes

by Z. Galewski

Faculty of Chemistry, University of Wrocław, 14, Joliot-Curie, 50-383 Wrocław, Poland

(Received February 22nd, 1999; revised manuscript April 4th, 1999)

Three new groups of unsymmetrically alkyloxyazobenzenes (4-pentyloxy-4¢-alkyloxyazobenzenes, 4-hexyloxy-4¢-alkyloxyazobenzenes and 4-heptyloxy-4¢-alkyloxyazobenzenes) are presented for the alkyloxy chain length up to octadecyloxy. In each investigated compound the liquid crystalline mesophase, mainly nematic, was found. For compounds with long alkyloxy chains, smectic C, smectic I and smectic A were detected. Based on the DSC, polarizing microscopy and thermo-optics the phase transitions were characterized and entropy was tested as the parameter, which does not depend on the molecular





Kinetics of the Hydrogen Chloride/Methanol-Catalyzed Mutarotation Reaction of N-(p-Chlorophenyl)-b-D-glucopyranosylamine

by K. Smiataczowa

Faculty of Chemistry, University of Gdańsk, ul. Sobieskiego 18, 80-952 Gdańsk, Poland

(Received December 8th, 1997; revised manuscript April 6th, 1999)

The rate of hydrogen chloride-catalyzed mutarotation reaction of N-(p-chlorophenyl)-b-D-glucopyranosylamine has been studied polarimetrically in absolute methanol at 25°C. Depending on the HCl concentration, conversion of isomer b to isomer a  has been found to be either a simple pseudo-first order reaction or a complex process involving two parallel first-order reactions producing a common product. The rate constants of the reactions and their dependence on hydrogen ion concentration have been determined. It was demonstrated that a relatively stable N-glucoside×H+ cation was an intermediate product. Elementary rate constants for two reversible steps of the reaction have been determined, as well.





Electrochemical Studies of Trilayers
of Conducting Polymers

by K. Żabczyńska and K. Maksymiuk

Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warszawa, Poland

(Received March 3rd, 1999; revised manuscript April 20th, 1999)

Trilayer systems of conducting polymers consecutively coated on electrodes were studi-
ed in electrolyte (1 M KCl) solutions, using voltammetric and additionally chronoamperometric techniques. The trilayers were composed of polypyrrole doped with poly(4-styrenesulfonate) (PPy(PSS)) or perchlorate ions (PPy) as well as of poly(N-methylpyrrole) doped with perchlorates (PMPy). Charge trapping effects found in these systems were studied by comparing oxidation/reduction charges of trilayers with such charges for single polymeric layers. For trilayers (inner layer/central/outer layer) PMPy/PPy(PSS)/PMPy and PPy(PSS)/PMPy/PPy(PSS) the PPy(PSS) was found to be trapped in the oxidized state. It cannot be effectively oxidized/reduced due to limited ionic and electronic conductivity of reduced PMPy. For trilayers PPy/PMPy/PPy and PMPy/PPy/PMPy the effect of charge trapping is observed for PPy and results from low conductivity of reduced PMPy.





Acid Properties of HY Zeolite Dealuminated by Steaming and EDTA Treatment – NMR, XPS and IR Studies

by J. Datka1, B. Gil1, J. Złamaniec1, P. Batamack2, J. Fraissard2 and P. Massiani3

1Faculty of Chemistry, Jagiellonian University, 30-060 Cracow, Ingardena 3, Poland
E-mail: datka@trurl.ch.uj.edu.pl
2Laboratoire de Chimie des Surfaces (UPESA 7069 du CNRS) and 3Laboratoire de Réactivité de Surface (UMR 7609 du CNRS), Université Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05, France

(Received February 5th, 1999; revised manuscript April 26th, 1999)

Steaming of zeolite is known to remove some Al atoms from the framework, which results in the formation of extraframework Al species and in the increase of the framework Si/Al ratio (Si/Alfram). The effects of these factors on the nature, concentration, strength, homogeneity and accessibility of the acid sites in Y zeolite were followed by an IR study of the adsorption/desorption of ammonia and pyridine. The status of Si and Al atoms on the surface and in the bulk was followed by XPS and 29Si and 27Al MAS NMR spectroscopies. The effect of the extraframework Al was shown by comparing two HY zeolites with the same Al contents (non dealuminated HY1 and steamed HY1S, Si/Alglobal = 2.6), but the second one containing extraframework Al. The effect of Si/Alfram was deduced from the comparison of HY1 (Si/Alfram = 2.6) with dealuminated HY2SD (steamed then EDTA treated, Si/Alfram = 11.4) both samples being free of extraframework Al. The interaction of bridging hydroxyls with non framework Al, present as Lewis sites in steamed zeolites, generates a high acidity. Moreover, the strongly acidic Lewis sites (PyL band at 1452 cm–1), formed by steaming, are shown to be similar to those observed in dehydroxylated HY and they correspond to Al species strongly interacting with the framework.





A post Hartree-Fock Quantum-Chemical Study
of the Dimerization of 2-Pyrrolidinone

by L. Gorb, J. Jadżyn and K.W. Wojciechowski

Institute of Molecular Physics, Polish Academy of Sciences,
Smoluchowskiego 17, 60-179 Poznań, Poland

(Received April 13th, 1999; revised manuscript April 30th, 1999)

Results of an ab initio post Hartree-Fock study of the molecular structure, the relative stability, and the dipole moment of the hydrogen-bonded 2-pyrrolidinone dimers are reported. The geometries of local minima were optimized at the second-order MØller-Plesset perturbation theory level. The standard 6-31+G(d,p) basis set was used. The local minima were verified by calculations of the matrix of the second derivatives of the energy for the reoptimized HF/6-31+G(d,p) geometry. The single point calculations were performed at the MP4(SDQ)/6-31+G(d,p)//MP2/6-31+G(d,p) level of theory. Two types of stable 2-pyrrolidinone cyclic dimers of quite different polarity (0.14 D, and 2.2 D) have been found.





Effects on the Micellar Solubilization of Organic
Compounds by Surfactant Micelles. II.
Nature and  Position of Substituent Groups
in Aromatic Acids

by W.S. Higazy and F.Z. Mahmoud

Chemistry Department, University College for Girls, Ain-Shams University, Heliopolis, Cairo, Egypt

(Received February 16th, 1998; revised manuscript May 6th, 1999)

The semiequilibrium dialysis method has been used to  determine the  equilibrium of solubilization of o-, m- and p-toluic acids in micelles of the cationic surfactant 1-hexadecylpyridinium chloride (CPC) in 0.1 M HCl, in a range of concentrations of the toluic acids and surfactant.   Apparent solubilization constants, K, of the neutral acids have been correlated with mole fractions XA of the acid in the micelle. Several conclusions could be drawn from this study: (a) For each of the three toluic acid–CPC systems, K is found to vary near linearly with XA. (b)  Methyl and carboxyl groups as substituents in the benzene ring enhance the solubilization much more than the additive effect of both groups, when present separately. (c) The position of the substituent groups affects the extent of solubilization of the acids investigated.





Predictions of Mixed-Gas Adsorption Equilibria
from Pure Component Adsorption Data:
A Comparative Study of the
Integral Equation Approaches

by K. Nieszporek

Department of Theoretical Chemistry, Maria Curie-Sklodowska University, 20-031 Lublin, Poland

(Received January 27th, 1999; revised manuscript May 14th, 1999)

Theoretical predictions of mixed-gas adsorption, based on the knowledge of single-gas adsorption, create a great challenge. The possibilities of the IE (Integral Equation) approach to solve that important theoretical problem are examined. A special attention is given to possibilities of arriving at relatively simple analytical or combined analytical/numerical solutions.





Crystal and Molecular Structure
of 2-{
o-Phenylene-[1-(o-phenyleneamino)ethyl]imino}-4-
-methylquinoline

by Z. Karczmarzyk1,  T. Kopeæ2 and J. Lewiński2

1Department of Chemistry, Agricultural and Teachers University, ul. 3 Maja 54,08-110 Siedlce, Poland

2Department of Chemistry, Warsaw University of Technology, ul. Noakowskiego 3, 00-664 Warszawa, Poland




(Received October 23rd, 1998; revised manuscript April 22nd, 1999)



Synthesis and Structure of Diiodo(phthalocyaninato(2-))tin(IV)

by J. Janczak and R. Kubiak

W. Trzebiatowski Institute of Low Temperatures and Structure Research,
Polish Academy of Sciences,  P.O. Box 1410, 50-950 Wrocław, Poland
Email:  janczak@highscreen.int.pan.wroc.pl

(Received March 15th, 1999; revised manuscript April 26th, 1999)


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