LnIII] (Ln = Gd, Tb, Ho, Er, Y)
POLISH JOURNAL OF CHEMISTRY
Volume 73 Number 10 October 1999
Pages 1595-1756
CONTENTS
Peculiarities of the Interaction Between Components in the Systems Containing Rare Earth Metals, Transition Metals and Phosphorus
- Chykhrij S.I.
Isonucleosides. Synthesis and Biological Activity
- Walczak K.
Thermodynamics of Solubility of Solids in Liquids
- Buchowski H. and Książczak A.
INORGANIC CHEMISTRY
Synthesis, Characterization and Magnetic Properties of Tetracarboxylato-Bridged Binuclear Cobalt(II) Complexes
- Li Y.T., Yan C.W. and Kong X.H.
Synthesis and Magnetic Properties of m-Chloranilato-Bridged Binuclear Iron(II) Complexes
- Li Y.T., Yan C.W. and Zeng X.C.
X-ray Investigation of the Ce–Cu–Cd System at 570 K
- Horechyy A.I., Pavlyuk V.V. and Bodak O.I.
ORGANIC CHEMISTRY
Crystal Structure of Molecular Complex (R)-(+)-3-Cyclohexene-1-carboxylic Acid with Brucine
- Krajewski K. and Ciunik Z.
Cyclic Analogues of Proline-Rich Protein Fragments. Part II: Conformational Studies Using NMR Spectroscopy and Theoretical Conformational Analysis
- Rodziewicz S., Wirkus-Romanowska I., Ciurak M., Miecznikowska H., Kupryszewski G., Czaplewski C., Liwo A. and Rolka K.
Synthesis and Properties of Azoles and Their Derivatives. Part XLI. Stereoselectivity and Kinetic Study of the [2+3]Cycloaddition of E-b-Nitrostyrene to Z-C,N-Diphenylnitrone
- Barański A.
Structural Studies of Some Mesoionic 1,3-Diphenyl-1,2,3,4-tetrazolium-5-aminides by Nitrogen NMR Techniques
- Jaźwiński J.
The Studies on the Synthesis and DNA Intercalative Properties of a New Type of Anthracene Probes Possessing Crown Ethers and Uracyl Groups
- Ostaszewski R., Wilczyńska E. and Wolszczak M.
PHYSICAL CHEMISTRY
The Role of Lewis Acid – Lattice Oxygen Reaction in Solid Superacids Formation
- Marczewski M., Marczewska H. and Witosławski K.
Kinetics and Mechanism of the Reaction Between 2,3,5,6-Tetrabromo-1,4-benzoquinone and Tetramethylguanidine in Benzene
- Dworniczak M. and Jarczewski A.
COMMUNICATIONS
Synthesis, Spectrometry and Magnetism of Novel m-Oxamido Heterotrinuclear
Complexes [LnIII] (Ln = Gd, Tb, Ho, Er, Y)
- Li X.Y., Xu J.Y., Hao L.F., Shen H.Y., Jiang Z.H. and Liao D.Z.
Synthesis and Spectroscopic Characterization of Addition Complexes of Copper Dithiophosphates with Heterocyclic Nitrogen Donor Bases
- Tripathi U.N., Mirza R., Bipin P.P. and Chaturvedi A.
1595
Peculiarities of the Interaction Between Components
in the Systems Containing
Rare Earth Metals,
Transition Metals and Phosphorus
by S.I. Chykhrij
Ivan Franko L’viv State University, Analytical Chemistry Department,
Kyryla
& Mefodiya Str. 6, L’viv 290005, Ukraine
(Received January 25th, 1999; revised manuscript March 19th, 1999)
A review of phase diagrams of ternary systems R–M–P (where: R = Sc, Y, La, Ce–Lu; M = transition metals) and crystal structures of the ternary compounds in order to determine the coordination of phosphorus atoms is carried out. Peculiarities of the interaction between components in the R–M–P systems are discussed. Types of coordination polyhedra of phosphorus and metal atoms and their correlation with phosphorus content in ternary phosphides are described and some generalizations and predictions concerning the interaction in the R–M–P systems are proposed.
1613
Isonucleosides. Synthesis and Biological Activity
by K. Walczak
Institute of Organic Chemistry and Technology, Silesian Technical University,
Krzywoustego
4, 44-100 Gliwice, Poland
(Received April 6th, 1999; revised manuscript May 6th, 1999)
Synthesis of isonucleosides, compounds with the heterocyclic base placed at non-anomeric position is discussed. Such derivatives are synthesized either by nucleophilic substitution of a leaving group by activated base or by construction of heterocyclic system at the amino group present at the sugar ring. Alternative pathways of synthesis contain addition of heterocyclic base to the a,b-unsaturated carbonyl sugar derivatives or 1,3-dipolar cycloaddition. Some examples of isonucleosides biological activity are described.
1631
Thermodynamics of Solubility of Solids in Liquids
by H. Buchowski and A. Książczak
Department of Chemistry, Warsaw University of Technology
Noakowskiego 3,
00-664 Warsaw, Poland
(Received April 28th, 1999; revised manuscript June 4th, 1999)
The most important results of the experimental and theoretical studies
of solid – liquid – vapor equilibria carried out in the Department of Physical
Chemistry at Warsaw University of Technology between 1975–1995 are reported.
The thermodynamic expressions for the solvent activity, the solubility
and the excess functions of mixing along the liquidus of an eutectic system
have been derived by integration of Gibbs-Duhem relation. The solubility
of a solid A in a liquid B depends on the melting temperature and the entropy
of fusion of A as well as on two constants l and b characterizing the solution;
l = 
, b is related to the heat capacity of solution. The methods of determination
of l and b from vapor pressure and solubility data are given. The experimental
excess Gibbs energy along the liquidus determined without any adjustable
parameter from solute and solvent activities in saturated solutions and
solubility agrees very well with the calculated curve. The excess enthalpy
and the excess entropy along the liquidus show the presence of a short–range
order in liquid A. The destruction of the order by mixing with an inert
solvent involves positive contributions to the excess enthalpy and the
excess entropy. Sometimes both shares cancel out and the solution behaves
as the pseudo-ideal one. The conditions of validity of Schröder or Malesiński
ideal solubility equations are formulated. The test of thermodynamic consistency
of solubility data and the method of detection of phase transitions are
proposed. It is shown that the fundamental assumption of regular solution
theory is wrong.
1665
Synthesis, Characterization and Magnetic Properties
of Tetracarboxylato-Bridged
Binuclear
Cobalt(II) Complexes
by Y.-T. Li1, C.-W. Yan2 and X.-H. Kong1
1Department of Chemistry, Qufu Normal University, Qufu Shandong, 273165,
P. R. China
2Department of Biology, Qufu Normal University, Qufu Shandong,
273165, P. R. China
(Received March 8th, 1999; revised manuscript May 11th, 1999)
Four new cobalt(II) binuclear complexes, described by the overall formula
[Co2(PMTA)L4], where L denotes 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy);
5-methyl-1,10-phenanthroline (Me-phen); 5-chloro-1,10-phenanthroline (Cl-phen);
5-bromo-1,10-phenanthroline (Br-phen) and PMTA represents the tetraanion
of pyromellitic acid, have been synthesized and characterized by elemental
analyses, molar conductivity measurements and spectroscopic (electronic
and IR spectra) studies. It is proposed that these complexes have PMTA-bridged
structures and consist of two cobalt(II) ions, each in a distorted octahedral
environment. The complexes [Co2(PMTA)(Me2-bpy)4] (1) and [Co2(PMTA)(Me-phen)4]
(2) were further 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, 
, giving the exchange
parameters J = –1.16 cm–1 for (1) and –1.21 cm–1 for (2). The result indicates
that there is a very weak antiferromagnetic spin-exchange interaction between
the two Co(II) ions within each molecule.
1673
Synthesis and Magnetic Properties
of µ-Chloranilato-Bridged Binuclear
Iron(II)
Complexes
by Y.-T. Li1, C.-W. Yan2 and X.-C. Zeng3
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, Sichuan University, Chengdu,
Sichuan, 610064, P. R. China
(Received March 12th, 1999; revised manuscript May 11th, 1999)
Five new µ-chloranilato-bridged binuclear iron(II) complexes of the formula
[Fe2(CA)L4](ClO4)2 [L denotes 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy);
5-chloro-1,10-phenanthroline (Cl-phen); 5-bromo-1,10-phenanthroline (Br-phen);
1,10-phenanthroline (phen) and 5-nitro-1,10-phenanthroline (NO2-phen)],
where CA represents the dianion of chloranilic acid, have been synthesized
and characterized. Based on elemental analyses, molar conductivity, magnetic
moment of room-temperature measurements and spectroscopic studies, it is
proposed that these complexes have CA-bridged structures and consist of
two iron(II) ions, each in a distorted octahedral environment. The complexes
[Fe2(CA)(phen)4](ClO4)2 (1) and [Fe2(CA)(Me2-bpy)4](ClO4)2 (2) were further
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, 
, giving the exchange parameter
J = –7.5 cm–1 for (1) and J = –4.6 cm–1 for (2). This result indicates
that there is a weak antiferromagnetic spin-exchange interaction between
the two Fe(II) ions within each molecule.
1681
X-ray Investigation of the Ce–Cu–Cd System at 570 K
by A.I. Horechyy, V.V. Pavlyuk and O.I. Bodak
Department of Inorganic Chemistry, Ivan Franko Lviv State University,
Kyryla
and Mefodia str. 6, 290005, Lviv, Ukraine
(Received May 5th, 1999; revised manuscript June 15th, 1999)
An isothermal section of the phase diagram of Ce–Cu–Cd system at 570 K was investigated by X-ray method. Six ternary compounds were found. The structure of CeCuCd compound is a derivative from a CeCd2 structure type.
1687
Crystal Structure of Molecular Complex (R)-(+)-3-Cyclohexene-1-carboxylic Acid with Brucine
by K. Krajewski and Z. Ciunik
Faculty of Chemistry, Wrocław University, F. Joliot-Curie 14, 50-383 Wrocław,
Poland
E-mail: kris@wchuwr.chem.uni.wroc.pl
(Received February 24th, 1999; revised manuscript May 5th, 1999)
The 3-cyclohexene-1-carboxylic acid was prepared and resolved with brucine. Absolute configuration of (R)-(+)-3-cyclohexene-1-carboxylic acid was confirmed by X-ray diffraction methods.
1697
Cyclic Analogues of Proline-Rich Protein Fragments.
Part II: Conformational
Studies Using NMR
Spectroscopy and Theoretical Conformational Analysis
by S. Rodziewicz, I. Wirkus-Romanowska, M. Ciurak, H. Miecznikowska,
G.
Kupryszewski, C. Czaplewski, A. Liwo and K. Rolka
Faculty of Chemistry, University of Gdańsk, Sobieskiego 18, PL-80-952 Gdańsk, Poland
(Received April 6th, 1999; revised manuscript May 10th, 1999)
The solution structures in DMSO-d6 of two cyclic analogues of proline-rich protein (PRP) fragments:
Cys1-Val-Glu-Ser-Tyr-Val-Pro-Leu-Phe-Pro-Cys11
Ac-Glu1-Tyr-Val-Pro-Leu-Phe-Pro-Lys8-NH2 with immunotropic activity has been investigated by 1D and 2D NMR spectroscopy and total conformational analysis. These peptides were designed based on the immunoregulatory activity of linear peptides obtained after chymotrypsin digestion of PRP. Despite the fact that the structures of both analogues cannot be interpreted in terms of a single conformation, the superposition of the most populated conformations of the cyclic peptides studied revealed a similar geometry for the Tyr-Val-Pro-Leu-Phe-Pro fragment (RMSD = 1.6 Å) in both peptides and therefore might be considered to be responsible for the biological activity.
1711
Synthesis and Properties of Azoles and Their Derivatives.
Part XLI. Stereoselectivity
and Kinetic Study
of the [2+3]Cycloaddition of E-b-Nitrostyrene
to Z-C,N-Diphenylnitrone
by A. Barański
Institute of Organic Chemistry and Technology, Technical University,
ul.
Warszawska 24, 31-155 Cracow, Poland
(Received April 9th, 1999; revised manuscript May 24th, 1999)
Stereoselectivity and the kinetics of the reaction of E-b-nitrostyrene to Z-C,N-diphe- nylnitrone at different temperatures and in several solvents have been studied. From the results obtained, it is evident that the reaction shows the properties of a one-step concerted process, so that it can be considered a typical [2+3]cycloaddition process.
1719
Structural Studies of Some Mesoionic 1,3-Diphenyl-1,2,3,4-tetrazolium-5-aminides
by
Nitrogen NMR Techniques
by J. Jaźwiński
Institute of Organic Chemistry, Polish Academy of Sciences,
ul. Kasprzaka
44/52, 01-224 Warszawa 42 POB 58, Poland
(Received May 4th, 1999; revised manuscript May 25th, 1999)
The 14N and 15N NMR data for some 1,3-diphenyl-1,2,3,4-tetrazolium-5-aminides are reported. A typical 15N NMR spectrum consists of five signals, laying within the ranges: –172 to –192 ppm (N1), –56 to –61 ppm (N2), –103 to –106 ppm (N3), –122 to –129 ppm (N4) and –155 to –260 ppm (N6). The 14N NMR data suggest the positive charge localization mainly on the N3 ring atom. Protonation of the molecule occurring at the exocyclic N6 atom results in the change of the 15N chemical shifts of all nitrogen atoms: 9 to 23 ppm for N1, 18 to 25 ppm for N2, 4 to 6 ppm for N3, 5 to 15 ppm for N4 and –70 to –102 ppm for N6 atom, respectively. Synthesis of three new mesoionic compounds, 5-(4-methoxyaniline)-1,3-diphenyl-1,2,3,4-tetrazole 7, 5-(N-cyclohexylamine)-1,3-diphenyl-1,2,3,4-tetrazole 8 and 5-(N-methylamine)-1,3-diphenyl-1,2,3,4-tetrazole 9 are reported.
1725
The Studies on the Synthesis and DNA Intercalative
Properties of a New Type
of Anthracene Probes
Possessing Crown Ethers and Uracyl Groups
by R. Ostaszewski1, E. Wilczyńska2 and M. Wolszczak2
1Institute of Organic Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52,
01-224 Warszawa, Poland
2Institute of Applied Radiation Chemistry, Technical
University of ŁódŸ,
Wróblewskiego 15, 93-590 ŁódŸ, Poland
(Received May 6th, 1999; revised manuscript May 26th, 1999)
A new procedure for the synthesis of aminoanthracene DNA probe 1 was developed. The model studies on the influence of protective groups on the reaction course towards formation of aminoanthracene 3a were performed. The results of these studies were utilized in the synthesis of anthracene crown ether 10a. Binding studies of this compound show low affinity (K = 2.3´10–1 M–1) of this probe to CT-DNA. Smaller binding constant of this compound as compared to compound 3a is presumably caused by complexation of sodium cation from the buffer. The model studies towards incorporation of uracyl group into aminoanthracene 10a by formation of amide bonds were performed. The reaction proceeds only in the presence of p-nitrophenyl leaving group.
1733
The Role of Lewis Acid – Lattice Oxygen Reaction
in Solid Superacids Formation
by M. Marczewski, H. Marczewska and K. Witosławski
Warsaw University of Technology, Faculty of Chemistry, Koszykowa 75, 00-662 Warsaw, Poland
(Received March 26th, 1999; revised manuscript May 18th, 1999)
Two reactions are responsible for superacid properties of SbF5(BF3)-carrier catalysts. The reaction between surface OH groups and SbF5(BF3) results in Brönsted acids centres formation. Lewis acid adsorption on O2– diminishes the basicity of the surface enhancing the acid strength of Brönsted sites.
1739
Kinetics and Mechanism of the Reaction
Between 2,3,5,6-Tetrabromo-1,4-benzoquinone
and
Tetramethylguanidine in Benzene
by M. Dworniczak and A. Jarczewski
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780
Poznan, Poland
e-mail: dworn@main.amu.edu.pl.
(Received March 15th, 1999; revised manuscript May 26th, 1999)
The reaction of bromanil (2,3,5,6-tetrabromobenzoquinone) with 1,1,3,3-tetramethyl- guanidine in benzene has been studied spectrophotometrically. The reaction proceeds according to the mechanism of vinylic substitution with a charge-transfer complex as the intermediate compound. The final product is a disubsituted quinone. The reaction mechanism is discussed.
1745
Synthesis, Spectrometry and Magnetism of Novel m-Oxamido Heterotrinuclear
Complexes
[
LnIII] (Ln = Gd, Tb, Ho, Er, Y)
by Xiao-Ying Li1, Jing-Yuan Xu1, Lan-Fang Hao1, Hao-Yu Shen2,
Zong-Hui Jiang2
and Dai-Zheng Liao2
1Department of Medicine, Tianjin Medical University, Tianjin 300203, P.R.
China
2Department of Chemistry, Nankai University, Tianjin 300071, P.R.
China
(Received December 17th, 1998; revised manuscript March 30th, 1999)
1751
Synthesis and Spectroscopic Characterization
of Addition Complexes of Copper
Dithiophosphates with Heterocyclic Nitrogen Donor Bases
by U.N. Tripathi1, Bipin P.P., R. Mirza1 and A. Chaturvedi2
1School of Studies in Chemistry, Vikram University, Ujjain - 456 010, India
2Department of Chemistry, Govt. P.G. College, Ajmer, India
(Received December 28th, 1998; revised manuscript May 18th, 1999)
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