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PL ISSN 0137-5083

POLISH      
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Volume 71 Number 4 April 1997
Pages 407-524

 
   


Polish Chemical Society 

  

CONTENTS

 


Page

REVIEW ARTICLE
407 Reaction of the Hydrogen Electrode in Molten Alkali Carbonates
- Suski L.


INORGANIC CHEMISTRY
428 Clathrochelate Tin-containing Iron(II) Dioximates Formed by Tin Bromide and Fluoride: Synthesis and Spectra
- Voloshin Y.Z., Trachevskii V.V. and Polshin E.V.
436 Preparation, Properties and Thermal Decomposition of Silver(I) Complexes with Pyridinedicarboxylic Acids
- Brzyska W. and Ozga W.


ORGANIC CHEMISTRY
441 A 13C, 15N and 77Se NMR Study of Some Seleno and Diseleno Azines and Related Compounds
- Bernatowicz P., Stefaniak L., Giurg M., Syper L. and Webb G.A.
446 A 15N NMR Study of Three 5,10-Dihydrophenophosphazines
- Skolimowski J., Schilf W., Stefaniak L. and Webb G.A.
449 Preparation and Reactions of 5-Nitromethyl-gamma-tocopherol Acetate
- Witkowski S., Markowska A. and Walejko P.
454 Alkyl Migrations in the Thermal Transformation of 2,6-Dialkoxy-7,9-dimethylpurinium Iodides Leading to 1,3,7-Trialkylxanthines
- Kowalska A. and Maslankiewicz A.


PHYSICAL CHEMISTRY
460 Polarizabilities and Diamagnetic Susceptibilities of Cyclohexane Liquid Crystals
- Narasimha Murthy Y., Rama Murthy V. and Ranga Reddy R.N.V.
467 Modelling of Bistable Chemical System by Cellular Automata Technique
- Frankowicz M. and Kawczynski A.L.
474 Perborate Oxidation of Iodide Ion
- Karunakaran C., Muthukumaran B. and Kamalam R.
480 Monte Carlo Simulation of Associating Fluid with Two Bonding Sites in Slit-Like and Spherical Pores
- Borowko M., Sokolowski S. and Zagorski R.


CRYSTAL AND MOLECULAR STRUCTURES
488 6-Azido-1,2,3,4-tetrazolo-[1,5-b]-pyridazine
- Katrusiak A.S., Gdaniec M. and Katrusiak A.A.
493 A Pyrazine-Bridged Chain Structure of Magnesium Complex with Pyrazine-2,3-dicarboxylic Acid
- Ptasiewicz-Bak H. and Leciejewicz J.
501 Crystal and Molecular Structure of [Fe3O(C6H5COO)6(H2O)3].
3-Cl-PyH.(CH3C6H4SO3)2.2H2O
- Cadelnic I., Shova S., Simonov Ya.A., Cendrowska E., Gdaniec M., Jovmir T., Turta C. and Bulhac I.


COMMUNICATIONS
509 Acetylenes in Agrobacterium rhizogenes Transformed Root Culture of Tanacetum parthenium
- Stojakowska A. and Kisiel W.
513 Complexes of 2,4'-Bipyridyl with Various Salts of nd10 Metals
- Czakis-Sulikowska D., Radwanska-Doczekalska J., Markiewicz M., Pustelnik N. and Kuznik B.
519 Thermal Rearrangement of 4-Alkoxy-3'-alkylthio-3,4'-diquinolinyl Sulfides to 1-Alkyl-1,4-dihydro-4-oxo-3'-alkylthio-3,4'-diquinolinyl Sulfides
- Boryczka S. and Maslankiewicz A.
522 The Concept of an "Energetic Ladder" as a Possible Step Sequence for Large Energetic Transitions
- Baranowski B.


ABSTRACTS

 

Pages

407-427

Reaction of the Hydrogen Electrode
in Molten Alkali Carbonates

by L. Suski
Institute of Physical Chemistry of the Polish Academy of Sciences,
Molten Salts Laboratory, ul. Zagrody 13, 30-318, Krakow, Poland

(Received September 26th, 1996; revised manuscript December 16th, 1996)

Nowadays fuel cells with molten alkali carbonates as electrolytes (Molten Carbonate Fuel Cells) are extensively developed, especially in USA and Japan, in order to produce electric power in 1-100 MW plants. In these devices a gas mixture of H2, CO, CH4, (containing also CO2 and H2O, the C-H-O gas mixture), is used as fuel to feed porous anodes based on nickel. On these anodes only hydrogen is oxidized in a direct electrochemical process. Electrochemical equilibria in systems: molten carbonates + fuel gas mixture at metallic electrodes, as well as kinetics of hydrogen electrode reaction in these electrolytes, have been extensively investigated during last decades. Papers concerning these topics are reviewed and conclusions formulated in the literature are presented and compared.

428-435

Clathrochelate Tin-containing Iron(II) Dioximates
Formed by Tin Bromide and Fluoride:
Synthesis and Spectra

by Y.Z. Voloshin, V.V. Trachevskii and E.V. Polshin
Karpov Institute of Physical Chemistry, 103064 Moscow, Russia

(Received October 28th, 1996; revised manuscript December 18th, 1996)

The reactions of encapsulation of iron(II) by template cross-linking of tris-dioximates with tin(IV) bromide and fluoride have been studied. The clathrochelate structures of synthesized complexes of the general composition (HAm)2[FeD3(SnX3)2] (where D2- is the dianion of the corresponding dioxime, X - fluoride or bromide, Am - organic amine) were confirmed by elemental analysis, IR, NMR ( 1H, 13C { 1H}, 19F, 119Sn) and Moessbauer (119Sn) spectra. The distorted trigonal antiprismatic coordination surrounding of iron(II) atom and electron density distribution was obtained from Moessbauer (57Fe) parameters. For synthesized clathrochelate complexes of methylglyoxime two isomers (fac and mer) have been identified from NMR (13C { 1H}, 119Sn) spectra.

436-440

Preparation, Properties and Thermal
Decomposition of Silver(I) Complexes
with Pyridinedicarboxylic Acids

by W. Brzyska and W. Ozga
Department of Inorganic and General Chemistry, Faculty of Chemistry,
Maria Curie Sklodowska University,
pl. M. Curie Sklodowskiej 2, 20-031 Lublin, Poland

(Received November 6th, 1996; revised manuscript January 6th, 1997)

Silver(I) complexes with isomers of pyridinedicarboxylic acids were prepared and studied. The IR spectra and X-ray diffractograms were recorded and their thermal decomposition in static air was investigated. During heating the hydrated complexes decompose to free silver directly (-2,6-, -3,5-) or with intermediate formation anhydrous of ones (-2,3-, -2,4-, -2,5-). The prepared complexes are sparingly soluble in water (10-4-10-5 mol dm-3).

441-445

A 13C, 15N and 77Se NMR Study of Some Seleno
and Diseleno Azines and Related Compounds

by P. Bernatowicz1, L. Stefaniak1 , M. Giurg2, L. Syper2
and G.A. Webb3
1Institute of Organic Chemistry, Polish Academy of Sciences,
PL-01-224 Warszawa, ul. Kasprzaka 44/52, Poland
2Institute of Organic Chemistry, Biochemistry and Biotechnology,
Technical University of Wroclaw, Wroclaw, Poland
3Department of Chemistry, University of Surrey,
Guildford, Surrey GU2 5XH, UK

(Received December 13th, 1996)

13C, 15N and 77Se NMR data are reported for eleven compounds. The chemical shifts are found to be fairly typical for the compounds studied. A number of one-, two- and three-bond spin-spin coupling values are given. These serve to enhance the previously spare data in particular for 2J(77Se-15N) and 3J(77Se-15N).

446-448

A 15N NMR Study of Three
5,10-Dihydrophenophosphazines

by J. Skolimowski1, W. Schilf2, L. Stefaniak2 and G.A .Webb3
1Department of Chemistry University of Lodz,
PL-90-136 Lodz, ul. Narutowicza 68, Poland
2Institute of Organic Chemistry, Polish Academy of Sciences,
PL-01-224 Warsaw, ul. Kasprzaka 44/52, Poland
3Department of Chemistry, University of Surrey, Guildford Surrey, GU2 5XH England

(Received December 13th, 1996)

15N NMR data are reported for three phenophosphazines. The results found for the 15N chemical shifts and 1J(15N-1H) couplings are consistent with the structures given for these compounds. The potential prototropic equilibrium anticipated for compound 1 is found not to occur in DMSO solution at room temperature.

449-453

Preparation and Reactions of
5-Nitromethyl-
gamma-tocopherol Acetate

by S. Witkowski, A. Markowska and P. Walejko
Institute of Chemistry, University of Warsaw Bialystok Branch,
Al. J. Pilsudskiego 11/4, 15-443 Bialystok, Poland

(Received July 24th, 1996; revised manuscript December 24th, 1996)

Nitration of alfa-tocopherol acetate 1b yielded 5-nitromethyl-gamma-tocopherol acetate 2b. The acetate 2b was converted to free phenol 2a by transesterification in methanol. Reduction of 2b by NaBH4 in ethyl acetate and methanol gave 5-(2-hydroxypropyl)-gamma-tocopherol 5a and 5-methoxymethyl-gamma-
-tocopherol 6 respectively.

454-459

Alkyl Migrations in the Thermal Transformation
of 2,6-Dialkoxy-7,9-dimethylpurinium Iodides
Leading to 1,3,7-Trialkylxanthines

by A. Kowalska and A. Maslankiewicz
Department of Organic Chemistry, Silesian School of Medicine,
Jagiellonska 4, 41-200 Sosnowiec, Poland

(Received December 17th, 1996; revised manuscript January 17th, 1997)

2,6-Dialkoxy-7,9-dimethylpurinium iodides 1 undergo thermal transformation to 1,3,7-trialkylxanthines 2 as a result of C6O>Nx, C2O> Nx, N9>Nx and N7>Nx (when x = 1, 3 or 7) alkyl group migration. Intra- or intermolecular character of rearrangement was studied using deuterium-labelled derivatives of 1, and by cross-over experiment with salts 1a* and 1c.
The 1H NMR spectra of 1,3,7-trialkylxanthines 2 (R = Me, Et) are presented.

460-466

Polarizabilities and Diamagnetic Susceptibilities
of Cyclohexane Liquid Crystals

by Y. Narasimha Murthy1, V. Rama Murthy2 and R.N.V. Ranga Reddy2
1Department of Physics, SSBN College, Anantapur - 515 001, (A.P.) India
2Department of Physics, S.K. University, Anantapur - 515 003, (A.P.) India

(Received May 22nd, 1996; revised manuscript January 2nd, 1997)

Mean molecular polarizabilities, polarizability anisotropies and diamagnetic susceptibilities of nematogenic homologous series of trans-4-alkyl(4-cyanophenyl)-cyclohexanes (ethyl, propyl, butyl, pentyl and heptyl) are estimated applying a new technique using infrared spectral data. A close agreement is found between the values estimated by the present method and the reported data.

467-473

Modelling of Bistable Chemical System
by Cellular Automata Technique

by M. Frankowicz1 and A.L. Kawczynski2
1Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Cracow, Poland
2Institute of Physical Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warsaw, Poland

(Received January 6th, 1997)

A simple and realistic model of a chemical system exhibiting bistability is studied by cellular automata approach. The obtained results are compared with solution of the master equation and molecular dynamics simulations.

474-479

Perborate Oxidation of Iodide Ion

by C. Karunakaran, B. Muthukumaran and R. Kamalam
Department of Chemistry, Annamalai University, Annamalainagar 608 002, India

(Received October 21st, 1996; revised manuscript January 7th, 1997)

In aqueous acidic solution perborate generates hydrogen peroxide and the oxidation of iodide ion to iodine at 35oC follows the rate law -d[oxidant]/dt = (0.367 [I-][H+] + 1.96x10-2[I-] + 9.78x10-4) [oxidant].
The mechanism of oxidation is discussed.

480-487

Monte Carlo Simulation of Associating Fluid
with Two Bonding Sites in Slit-Like and Spherical Pores

by M. Borowko, S. Sokolowski and R. Zagorski
Department for the Modelling of Physico-Chemical Processes, Faculty of Chemistry,
MSC University, 20031 Lublin, Poland, E-mail: malgosia@hebe.umcs.lublin.pl; http://hebe.umcs.lublin.pl

(Received September 19th, 1996; revised manuscript January 8th, 1997)

Monte Carlo simulations of adsorption of associating fluids in slit-like and spherical pores were performed assuming an orientational-dependent associating potential with two bonding sites. The simulations have indicated that the number of associates depends on the pore shape and is different in different parts of the system. Orientational ordering of the particles was also investigated. At the surface, the associates assume orientation parallel to the pore wall. The length of the clusters formed is different in different parts of the pore.

488-492

6-Azido-1,2,3,4-tetrazolo-[1,5-b]-pyridazine

by A.S. Katrusiak1,2, M. Gdaniec1 and A.A. Katrusiak3
1Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
2Instrumental Laboratory, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
3Faculty of Pharmacy, Karol Marcinkowski University of Medical Sciences,
Grunwaldzka 6, 60-780 Poznan, Poland

(Received November 4th, 1996)

3,6-Diazidopyridazine, C4H2N8, is present in the azido-tetrazole tautomeric form in the crystalline state. The crystals are isostructural with the crystals of 7-azido-1,2,3,4-tetrazolo-[1,5-a]-pyrimidine. The orientation of the azide substituent is identical in these compounds, but the pyridazine ring is stronger deformed compared to the pyrimidine analogue.

493-500

A Pyrazine-Bridged Chain Structure of Magnesium
Complex with Pyrazine-2,3-dicarboxylic Acid

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

(Received November 13th, 1996; revised manuscript December 18th, 1996)

Trisaquo(pyrazine-2,3-dicarboxylato) magnesium(II) monohydrate, MgC6H14N2O8 crystals are monoclinic, Cc, a = 8.444(2) Å, b = 18.153(4) Å, c = 7.416(1) Å, ß = 114.49(3) deg., Z = 4. The structure consists of molecular chains propagating in the [101] direction. Magnesium ions are bridged by the 2,3-pzdc molecules via the oxygen atom of the monodentate carboxylic group (Mg-O = 2.037 Å) on one side and a (N, O) moiety on the other side ( Mg-N = 2.246 Å, Mg-O = 2.056 Å). Three water molecules (mean Mg-O = 2.062 Å) complete a fairly regular octahedral enviroment around the magnesium ion. An extensive hydrogen bond system is responsible for the stability of the crystal.

501-508

Crystal and Molecular Structure of
[Fe3O(C6H5COO)6(H2O)3].3-Cl-PyH .(CH3C6H4SO3)2.2H2O

by I. Cadelnic1, S. Shova1, Yu. A. Simonov1, E. Cendrowska2, M. Gdaniec2,
T. Jovmir3, C. Turta3 and I. Bulhac3
1 Institute of Applied Physics of the Academy of Sciences of Moldova,
Academiei 5, Kishinev 20-28, Moldova
2Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
3Institute of Chemistry of the Academy of Sciences of Moldova,
Academiei 3, Kishinev 20-28, Moldova

(Received December 20th, 1996)

The crystal structure of the trinuclear iron(III) complex [Fe3O(C6H5COO)6(H2O)3].3-Cl-PyH.(CH3C6H4SO3)2.2H2O has been determined by X-ray crystallography. Crystals are monoclinic, space group C2/c, a = 14.281(3), b = 17.815(4), c = 25.844(5)Å, ß = 93.72(3) and Z = 4. The final R-value is 0.045 for 2940 reflections with I equal or greater than 2sigma(I). The complex cation [Fe3O(C6H5COO)6(H2O)3]+ is situated on a crystallographic two-fold axis and has a typical geometry of the trinuclear iron(III) compound with µ3-O bridge. The 3-Cl-PyH+ cation is disordered over two positions, in which it interacts via H-bond with the tosylate anion. This cation is also intercalated between phenyl rings of the two benzoate groups, indicating that ¶-¶-interactions may be of some importance in stabilizing this crystal structure. All structural fragments are connected via H-bonds into two-dimensional network.

509-512

Acetylenes in Agrobacterium rhizogenes
Transformed Root Culture of
Tanacetum parthenium

by A. Stojakowska and W. Kisiel
Department of Phytochemistry, Institute of Pharmacology,
Polish Academy of Sciences, Smetna 12, 31-343 Krakow, Poland

(Received November 14th, 1996)

513-518

Complexes of 2,4'-Bipyridyl with Various Salts
of nd10 Metals

by D. Czakis-Sulikowska, J. Radwanska-Doczekalska,
M. Markiewicz, N. Pustelnik and B. Kuznik
Institute of General and Ecological Chemistry, Technical University of Lodz,
90924 Lodz, Poland

(Received October 2nd, 1996; revised manuscript January 6th, 1997)

519-521

Thermal Rearrangement of 4-Alkoxy-3'-alkylthio-3,4'-
-diquinolinyl Sulfides to 1-Alkyl-1,4-dihydro-4-oxo-3'-
-alkylthio-3,4'-diquinolinyl Sulfides [1]

by S. Boryczka and A. Maslankiewicz
Department of Organic Chemistry, Silesian School of Medicine,
Jagiellonska 4, 41-200 Sosnowiec, Poland

(Received December 23rd, 1996; revised manuscript January 28th, 1997)

522-524

The Concept of an "Energetic Ladder" as a Possible
Step Sequence for Large Energetic Transitions

by B. Baranowski
Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland

(Received November 6th, 1996; revised manuscript February 3rd, 1997)


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© 1997 Polish Journal of Chemistry
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