POLISH JOURNAL OF CHEMISTRY
Volume 71 Number 11 November 1997
Pages 1511- 1641


CONTENTS

Page

INORGANIC CHEMISTRY
1511 Synthesis, Spectral and Magnetic Properties of m-Chloranilato Manganese(II) Binuclear Complexes
— Li Y.T., Yan C.W. and Liao D.Z.
1518 Preparation, Properties and Thermal Decomposition of Y(III) and Lanthanide(III) Complexes with 2-Amino-5-chlorobenzoic Acid
— Brzyska W. and Borzechowski K.
1525 Synthesis and Magnetic Studies of Dinuclear Nickel(II) Complexes through Isophthalato Bridge
— Yan C.W., Li Y.T. and Liao D.Z.
1532 CuGaSe2-Cu2GeSe3Section of the Quasiternary Cu2Se-Ga2Se3-GeSe2 System
— Olekseyuk I.D., Strok O.M. and Zmiy O.F.
1537 Isothermal Section of the Nd-Co-Si System at 870 K
— Salamkha P.
ORGANIC CHEMISTRY
1540 Synthesis of Some Novel Nitrogenous Visnagin Derivatives
— Elgamal M.H.A., Hanna A.G., Mekhael M.K.G. and Meyer C.
1548 Convenient Synthesis of S- and Se-(2,3,4,6-tetra-O-benzyl-D-glucopyranosyl)-phosphorothioate, Phosphoroselenoate and Phosphorodithioate
— Kudelska W.
PHYSICAL CHEMISTRY
1553 Molecular Dynamics Simulations of Oscillations in a Model Chemical System
— Gorecki J. and Kawczynski A.L.
1565 Partially Localized Adsorption of a Single Gas on an Energetically Homogeneous Adsorbent
— Garbacz J.K.
1572 Osmium(VIII) Catalyzed Oxidation of Dimethyl Sulfoxide by Diperiodatonickelate(IV) in Aqueous Alkaline Medium
— Nandibewoor S.T. and Hugar G.H.
1579 Isopiestic Investigations of Solid Samples of Cs2SO4
— Baranowski B. and Lunden A.
1585 Kinetic Network for Oxidative Dehydrogenation of Propane on Vanadia-Titania Catalysts
— Sloczynski J., Grabowski R., Wcislo K. and Grzybowska-Swierkosz B.
1594 Spectroscopic Studies of the Complexation of Iodine with 5,6,14,15-Dibenzo-1,4-dioxa-8,12-
-diazacyclopentadeca-5,14-diene

— Sadeghi S., Shamsipur M. and Elahi M.
CRYSTAL AND MOLECULAR STRUCTURES
1603 Two-Dimensional Molecular Layers in the Crystals of Calcium Complex with Pyrazine-2,3-
-dicarboxylic Acid

— Ptasiewicz-Bak H. and Leciejewicz J.
1611 Crystal and Molecular Structure of N-tert-butyl-3[4-(2-methoxyphenyl)-1-piperazinyl]-2-
-phenylpropanamide Dihydrochloride (WAY-100135)

— Fruzinski A., Karolak-Wojciechowska J., Mokrosz M.J. and Bojarski A.J.
1618 X-ray and Conformational Investigation of Isomeric Methyl 2,6-Anhydro-3-deoxy-hept-2- eneates
— Krajewski J.W., Banaszek A. and Mlynarski J.
COMMUNICATIONS
1624 Thermodynamic Parameters Characterizing 1-Nitroso-2-naphthol in the Two-Phase
Water-Nitrobenzene Extraction System

— Makrlik E. and Vanura P.
1627 Synthesis and Crystal Structure of Nickel(II) Complex of N-(2-Hydroxypropyl)propylenediamine
— Cheng P., Shi J.M., Liao D.Z., Yan S.P., Jiang Z.H., Wang G.L., Yao X.K. and Wang H.G.
1631 Synthesis and Characterization of Niobium(V) Complexes of Malanoanilic Acid Hydrazones
— Maravalli P.B. and Goudar T.R.
1635 Synthesis, Spectra and Magnetic Properties of Binuclear CuII-NiII Complexes with N,N'-
-Bis(benzoato)oxamido Copper(II)

— Liu B., Shi J., Yan S.P., Liao D.Z., Jiang Z.H.
and Wang G.L.
1640 IUPAC Recommendations on Nomenclature and Symbols.


ABSTRACTS


1511-1517

Synthesis, Spectral and Magnetic Properties of
miu-Chloranilato Manganese(II) Binuclear Complexes

by Y.-T. Li1, C.-W. Yan2 and D.-Z. Liao3
1Department of Chemistry, Qufu Normal University, Qufu Shandong, 273165, P. R. China
2Department of Biology, Qufu Normal University, Qufu Shandong, 273165, P. R. China
3Department of Chemistry, Nankai University, Tianjin, 300071, P. R. China

(Received June 16th, 1997)

Five new manganese(II) binuclear complexes have been synthesized, namely [Mn2(CA)L4](ClO4)2 [L denotes 2,2'-bipyridine (bpy); 1,10-phenanthroline (phen); diaminoethane (en); 1,3-diaminopropane (pn) and 1,2-diaminopropane (ap)], where CA represents the dianion of chloranilic acid. Based on elemental analyses, molar conductivity and room temperature magnetic moment measurements, spectroscopic studies, it is proposed that these complexes have CA-bridged structures and consist of two manganese(II) ions in a distorted octahedral environment. The complexes [Mn2(CA)(bpy)4](ClO4)2 (1) and [Mn2(CA)(phen)4](ClO4)2 (2) were characterized by variable temperature magnetic susceptibility measurements (4 ~ 300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 .S2, giving the exchange parameter J = -2. 8 cm-1 for (1) and J = -7.9 cm-1 for (2). This result indicates that there is a weak antiferromagnetic spin-exchange interaction between two the Mn(II) ions within each molecule.

1518-1524

Preparation, Properties and Thermal Decomposition
of Y(III) and Lanthanide(III) Complexes
with 2-Amino-5-chlorobenzoic Acid

by W. Brzyska and K. Borzechowski
Department of Inorganic and General Chemistry, Faculty of Chemistry, Marie Curie Sklodowska University, 20-030 Lublin, Poland

(Received March 20th, 1997; revised manuscript June 30th, 1997)

The rare earth (Y, La-Lu, without Pm) 2-amino-5-chlorobenzoates were prepared and their composition and solubilities in water at 293 K were determined (10-4-10-5 mol dm-3). The complexes were obtained as solids with a 1:3 molar ratio of metal to organic ligand with general formula Ln(C7H5NClO2)3.nH2O, where n = 4, 5, 7 and their IR spectra were recorded. The COO- group acts as bidentate chelating (La-Eu) or bidentate chelating and bridging ligand (Gd-Lu). During heating, the hydrated complexes lose some of their molecules of crystallization water in one step and then decompose either directly to oxides (Y, Ce, Ho-Lu) or with intermediate formation of oxochlorides LnOCl (La, Pr-Dy). The temperature of oxide formation decreases from La2O3 (1470 K) to Lu2O3 (1099 K), except of CeO2 (849 K).

1525-1531

Synthesis and Magnetic Studies of Dinuclear Nickel(II) Complexes through Isophthalato Bridge

by C.W. Yan1, Y.T. Li2 and D.Z. Liao3
1Department of Biology, Qufu Normal University, Qufu Shandong, 273165, P. R. China
2Department of Chemistry, Qufu Normal University, Qufu Shandong, 273165, P. R. China
3Department of Chemistry, Nankai University, Tianjin, 300071, P. R. China

(Received September 16th, 1996; revised manuscript July 24th, 1997)

Four novel nickel(II) binuclear complexes have been synthesized and identified as [Ni2(IPHTA)(L)4](ClO4)2, where IPHTA is the isophthalate dianion and L denotes 2,2'-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4'-dimethyl-2,2'-bipyridine (Me2bpy) and 5-nitro-1,10-phenanthroline (NO2-phen). Based on elemental analyses, molar conductance measurements, IR and electronic spectra studies, these complexes are proposed to have extended IPHTA-bridged structures and to consist of two nickel(II) ions, each in a distorted octahedral environment. The complexes [Ni2(IPHTA)(bpy)4](ClO4)2 (1) and [Ni2(IPHTA)(Me2bpy)4](ClO4)2 (2) were characterized by variable temperature magnetic susceptibility (4 ~ 300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 .S2, giving the exchange integral J = -17.8 cm-1 for (1) and J = -12.5 cm-1 for (2). These results are commensurate with antiferromagnetic interactions between the adjacent metal ions. The influence of different terminal ligands on magnetic interactions between the metals of this kind of complexes is also discussed.

1532-1536

CuGaSe2-Cu2GeSe3 Section of the Quasiternary
Cu2Se-Ga2Se3-GeSe2 System

by I.D. Olekseyuk, O.M. Strok and O.F. Zmiy
Department of Inorganic and Physical Chemistry, Volyn' State University,
Voli av. 13, Lutsk 263009, Ukraine

(Received May 20th, 1997; revised manuscript August 27th, 1997)

The interaction between CuGaSe2 and Cu2GeSe3 was studied using differential thermal, microstructural and X-ray analyses and measurements of microhardness. Polythermal CuGaSe2-Cu2GeSe3 section of the quasiternary Cu2Se-Ga2Se3-GeSe2 system has been constructed. The ranges of the solid solutions have been determined.

1537-1539

Isothermal Section of the Nd-Co-Si System at 870 K

by P. Salamakha
Department of Inorganic Chemistry, L'viv State University, Kyryla and Mefodiya str., 6, 290005 L'viv, Ukraine

(Received July 10th, 1997; revised manuscript September 1st, 1997)

Equilibrium phase diagram has been established from X-ray phase analysis for the ternary system Nd-Co-Si at 870 K and the crystal structure of the existing compounds has been studied by X-ray structure analysis.

1540-1547

Synthesis of Some Novel Nitrogenous Visnagin Derivatives

by M.H.A. Elgamal1, A.G. Hanna1, M.K.G. Mekhael1 and C. Meyer2
1Laboratory of Natural Products, National Research Centre, Dokki, Cairo, Egypt
2Institute fuer Organische Chemie, Universitaet Hannover, D-3000 Hannover 1, Germany

(Received February 10th, 1997; revised manuscript July 1st, 1997)

Reaction of visnagin-9-phenoxysulphonyl ester and visnagin-9-N-methylpiperazinylsulphonyl with some alkyl primary amines afforded corresponding 5-alkylimine derivatives. Some visnagin-9-sulphamyl ureas and khellol carbamates were also synthesized. Antimicrobial activity of some compounds prepared was studied.

1548-1552

Convenient Synthesis of S- and Se-(2,3,4,6-
-tetra-O-benzyl-D-glucopyranosyl)-phosphorothioate, Phosphoroselenoate and Phosphorodithioate

by W. Kudelska
Institute of Chemistry, Faculty of Pharmacy, Medical University of Lodz, 90-151 Lodz, Muszynskiego 1, Poland

(Received June 25th, 1997; revised manuscript July 7th, 1997)

Organic phosphorothioate 7, phosphoroselenoate 8 and phosphorodithioate 9 were glucosylated with 2,3,4,6-tetra-O-benzyl-D-glucopyranose derivatives 1-6. When the reaction was performed in the presence of boron trifluoride etherate, the products were S-alpha-glucosyl and Se-alpha-glucosyl phosphoroethers 10-12. O-Benzylated glucosyl halides 5-6 with alkylammonium salt of 9 afforded S-ß-glucosyl phosphorodithioate 13, which underwent the ß ->/<- alpha anomerization by boron trifluoride etherate into more stable alpha-derivatives.

1553-1564

Molecular Dynamics Simulations of Oscillations
in a Model Chemical System

by J. Gorecki and A.L. Kawczynski
Institute of Physical Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warsaw, Poland

(Received June 20th, 1997)

The results of molecular dynamics (MD) simulations for a simple, but realistic model of a chemical system exhibiting oscillatory behavior are presented. The period of oscillations and the phase portrait of the system obtained in simulations are in agreement with phenomenology. Two types of fluctuations seem to appear in simulations: at short time scale fluctuations depend on the size of the system, whereas at the long time scale they are related to the random motion of the MD trajectory in the phase space.

1565-1571

Partially Localized Adsorption of a Single Gas
on an Energetically Homogeneous Adsorbent

by J.K. Garbacz
Department of Physicochemistry of Surface, Polytechnical and Agricultural University,
85-326 Bydgoszcz, Poland and
Department of Physical Chemistry, L. Rydygier Medicine University,
85-094 Bydgoszcz, Poland

(Received June 27th, 1997)

The new variant of description of a single gas adsorption on an energetically homogeneous solid adsorbent has been formulated, assuming both a partial localization of adsorption phase and a fractal character of the adsorbent. The adsorption equation, resulting from the idea presented, contains, among others, the two isothermal constants: KH (Henry constant) and Km-l (admolecule localization constant,) whose one-to-one dependences on temperature make various-temperature data description possible. Isotherm pencils of four adsorption systems have been described on the basis of the model proposed.

1572-1578

Osmium(VIII) Catalyzed Oxidation of Dimethyl
Sulfoxide by Diperiodatonickelate(IV) in
Aqueous Alkaline Medium

by S.T. Nandibewoor and G.H. Hugar
P.G. Department of Studies in Chemistry, Karnatak University, Dharwad-580 003, India

(Received May 19th, 1997; revised manuscript July 3rd, 1997)

The title reaction is zero order in diperiodatonickelate(IV) (DPN) and fractional order both in [DMSO] and [OH-]. Periodate has a retarding effect on the reaction. Effects of added products, ionic strength, dielectric constant of the reaction medium and temperature on the reaction have been studied. A plausible mechanism has been proposed and reaction constants involved are derived. Monoperiodatonickelate(IV) (MPN) and [OsO4(OH)2]2- were understood to be the active species of oxidant and catalyst respectively.

1579-1584

Isopiestic Investigations of Solid Samples of Cs2SO4

by B. Baranowski1 and A. Lunden2
1Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland
2Department of Physics, Chalmers University of Technology, S-41 296 Goeteborg, Sweden

(Received June 13th, 1997; revised manuscript July 28th, 1997)

The uptake of water by solid Cs2SO4 was investigated at 298.2 K in air of constant water activity (isopiestic method). The kinetics of this uptake was determined in the range of water activities 0.770-0.774 and especially in the neighborhood of the saturated solution. The main purpose of this paper is to compare with previous similar measurements on CsHSO4 samples, that is comparison between systems with a congruent (Cs2SO4) or an incongruent character (CsHSO4), respectively. The stationary (equilibrium) water uptake was determined in the water activity range of 0.77-0.80.

1585-1593

Kinetic Network for Oxidative Dehydrogenation
of Propane on Vanadia-Titania Catalysts

by J. Sloczynski, R. Grabowski, K. Wcislo and B. Grzybowska-Swierkosz
Institute of Catalysis and Surface Chemistry Polish Academy of Sciences 30-239 Krakow, Poland

(Received July 9th, 1997; revised manuscript August 4th, 1997)

Oxidative dehydrogenation (ODH) of propane on vanadia-titania catalysts is described by a parallel-consecutive kinetic network: carbon oxides observed beside propene as the reaction products are formed mainly by successive combustion of propene and to the smaller extent by parallel to ODH total oxidation of propane. The selectivity to propene is controlled mainly by the rate of the propene oxidation. The consecutive oxidation of propene proceeds mainly by the reaction of the adsorbed propene intermediate without desorption and readsorption of propene to the gas phase. Addition of Rb to vanadia-titania catalysts decreases the values of rate constants of the various steps of the reaction, particularly those of the total combustion of propene and propane and leads also to the decrease in the activation energy of parallel total oxidation of propane. The lowering of the rate of total combustion accounts for the increase in the selectivity to propane of Rb-promoted catalysts as compared with the non-promoted ones.

1594-1602

Spectroscopic Studies of the Complexation of Iodine with 5,6,14,15-Dibenzo-1,4-dioxa-8,12-diazacyclo-
pentadeca-5,14-diene

by S. Sadeghi1, M. Shamsipur2 and M. Elahi3
1Department of Chemistry, Shahid Beheshti University, Tehran, Iran
2Department of Chemistry, Razi University, Kermanshah, Iran
3Department of Physics, Razi University, Kermanshah, Iran

(Received April 28th, 1997; revised manuscript August 18th, 1997)

The complex formation between iodine and 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene (DBDA15C4) has been studied spectrophotometrically in chloroform solution. The resulting charge transfer complexes characterized by microchemical analysis and IR spectroscopy are formulated as [(DBDA15C4)2I+]I3- and [(DBDA15C4)2I+]I-. The rate constant and stability constant for the formation of [(DBDA15C4)2I+]I3- were calculated as k = (2.71 +/- 0.04) x 10-2 min-1 and 5.25 +/- 0.05 M-1, respectively. The complex shows semiconducting properties. The activation energy was evaluated as 0.88 eV.

1603-1610

Two-Dimensional Molecular Layers in the Crystals
of Calcium Complex with Pyrazine-2,3-dicarboxylic Acid

by H. Ptasiewicz-Bak and J. Leciejewicz
Institute of Nuclear Chemistry and Technology, 03-195 Warszawa, ul. Dorodna 16, Poland

(Received May 22nd, 1997)

The crystals of diaquo(m-pyrazine-2,3-dicarboxylato)calcium(II) dihydrate are monoclinic, space group P21, a = 6.832(1) Å, b = 16.765(3) Å, c = 8.410(2) Å, ß = 106.53(3) deg. It contains two symmetrically independent Ca ions, each coordinated by one nitrogen and seven oxygen atoms. Calcium ions are bridged in the direction of the a axis by oxygen atoms belonging to a bidentate carboxylic group of the acid molecule. The bridging in the direction of the b axis is accomplished by the same carboxylic group and by the second, monodentate carboxylic group as well as by the nearest to it nitrogen atom of the pyrazine ring (N,O-bonding moiety). In addition, each calcium ion is coordinated by two water molecules. The mean Ca-O and Ca-N bond distances are 2.441 Å and 2.645 Å respectively. Molecular sheets parallel to the (001) plane can be visualized. They are held together by strong hydrogen bonds operating via two solvation water molecules located in the space between the sheets.

1611-1617

Crystal and Molecular Structure of N-tert-butyl-3[4-(2-methoxyphenyl)-1-piperazinyl]-2-phenylpropanamide Dihydrochloride (WAY-100135)

by A. Fruzinski1, J. Karolak-Wojciechowska1,
M.J. Mokrosz2 and A.J. Bojarski2
1Institute of General and Ecological Chemistry, Technical University, 90-924 Lodz, Poland
2Department of Medicinal Chemistry, Institute of Pharmacology, Polish Academy of Sciences,
31-343 Krakow, Poland

(Received June 3rd, 1997; revised manuscript July 7th, 1997)

The structure of racemic N-tert-butyl-3-[4-(2-methoxyphenyl)-1-piperazinyl]-2-phenyl-propanamide dihydrochloride (WAY-100135), a full 5-HT1A receptor antagonist, was solved. The formerly postulated model, which predicts topographic requirements for the formation of bioactive complexes with 5-HT1A receptors, was compared with the crystallographic conformation and those of the free molecule and the molecule in a simulated water environment, obtained via energy minimization by semiempirical AM1 method.

1618-1623

X-ray and Conformational Investigation of Isomeric Methyl 2,6-Anhydro-3-deoxy-hept-2-enoates

by J.W. Krajewski, A. Banaszek and J. Mlynarski
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

(Received November 25th, 1996; revised manuscript July 4th, 1997)

The structures of the title compounds of the D-lyxo (1) and D-arabino (2) configurations have been investigated by X-ray methods. The crystals of 1 are orthorhombic, space group P212121, and of 2 belong to monoclinic space group P21. The unit cell dimensions are: for 1 a = 8.1789(5), b = 12.2672(7), c = 16.3720(9) Å, and for 2 a = 9.0749(7), b = 6.5655(5), c = 16.3131(8) Å, ß = 103.58(1)o. Both structures were solved by direct methods, and refined by a full-matrix, least-squares procedure. The pyranose ring of 1 and 2 adopted 4H5 conformation slightly deviated in the second compound. Relatively strong intermolecular hydrogen bonds were observed in the crystal lattice of 2.

1624-1626

Thermodynamic Parameters Characterizing 1-Nitroso-2-
-naphthol in the Two-Phase Water-Nitrobenzene
Extraction System

by E. Makrlik1 and. P. Vanura2
1Department of Chemistry, Charles University, Faculty of Education,
M.D. Rettigova 4, 116 39 Prague 1, Czech Republic
2Department of Analytical Chemistry, Prague Institute of Chemical Technology,
Technicka 5, 166 28 Prague 6, Czech Republic

(Received June 3rd, 1997)

1627-1630

Synthesis and Crystal Structure of Nickel(II) Complex of N-(2-Hydroxypropyl)propylenediamine

by P. Cheng1, J.M. Shi1, D.Z. Liao1, S.P. Yan1, Z.H. Jiang1,
G.L. Wang1, X.K. Yao2 and H.G. Wang2
1Department of Chemistry, Nankai University, Tianjin 300071, P.R. China
2Central Laboratory, Nankai University, Tianjin 300071, P.R. China

(Received May 19th, 1997; revised manuscript July 14th, 1997)

1631-1634

Synthesis and Characterization of Niobium(V)
Complexes of Malanoanilic Acid Hydrazones

by P.B. Maravalli and T.R. Goudar
P. G. Department of Studies in Chemistry, Karnatak University, Dharwad-580003, India

(Received March 12th, 1997; revised manuscript July 31st, 1997)

1635-1639

Synthesis, Spectra and Magnetic Properties of
Binuclear CuII-NiII Complexes with
N,N'-Bis(benzoato)oxamido Copper(II)

by B. Liu, J. Shi, S.P. Yan, D.Z. Liao, Z.H. Jiang and G.L. Wang
Department of Chemistry, Nankai University, Tianjin 300071, P. R. China

(Received June 13th, 1997; revised manuscript August 18th, 1997)

1640

IUPAC RECOMMENDATIONS ON NOMENCLATURE AND SYMBOLS

  • Extension and revision of the nomenclature for spiro compounds
  • Extension and revision of the von Baeyer system for
    naming polycyclic compounds (including bicyclic compounds)
  • Revision on the Nomenclature of Inorganic Chemistry (II.2)
    Names For Inorganic Radicals


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