POLISH JOURNAL OF CHEMISTRY
Volume 74 Number 3 March 2000
Pages 291-446
INORGANIC CHEMISTRY
Reactivity of cis-Diaminedichloroplatinum(II) (cis-Platin) Towards Chromium(VI)
- Stawińska J., Staszak Z., Jezierska J., Cieślak-Golonka M. and Daszkiewicz M.
New Complexes of Samarium(III), Terbium(III) and Holmium(III) with Quercetin-5'-sulfonic Acid
- Kopacz M. and Nowak D.
Large Scale Structures in Multicellular Chemical Systems
- Masełko J.
Application of the Kamlet-Taft and Abraham Models in Chemistry of Coordination Compound in the Solutions
- Apostoluk W., Tłaczała T. and Duda L.L.
Spectrochemical Properties of Noncubic Transition Metal Complexes in Solution. XI. Angular Overlap Studies of Bis(oxalato)- and Bis(malonato)diaquachromate(III) Complexes in Aqueous Solution
- Kurzak K.
The Anodic Behavior of Silver in Concentrated Chloride Solutions
- Kołodziej B.
Synthesis and Magnetic Properties of m-Terephthalato Binuclear Chromium(III) Complexes
- Li Y.T., Zeng X.C. and Yan C.W.
Synthesis and Ferromagnetic Spin-Coupling in N,N'-Oxamidobis(benzoato)cuprate(II) Bridged Copper(II)Chromium(III) Heterobinuclear Complexes
- Li Y.T., Yan C.W. and Zeng X.C.
Synthesis, Characterization and Magnetism of Chloranilato-Bridged Chromium(III)Chromium(III) Binuclear Complexes
- Li Y.T., Yan C.W. and Zeng X.C.
Copper(I) Sulfamate p-Complexes: Synthesis and Crystal Structure of [{(CH2=CHCH2-)2N-CHO}Cu(NH2SO3)(H2O)] Compound
- Filinchuk Ya.E., Melnyk O.P. and Myskiv M.G.
PHYSICAL CHEMISTRY
The Influence of (O,N)-Deuteration on the Crystal and Molecular Structure, Thermal Stability and Spectroscopic Properties of 1,3-Propanediammonium Hydrogenphosphate Monohydrate
- Bartoszak-Adamska E., Figlerowicz M., Wiewiórowski M., Gustafsson T., Olovsson I. and Jaskólski M.
Deuterium Isotope Effects of o-Hydroxythioamides, 2D-Thiazolines and 5-Acyl-2-thiobarbituric Acids
- Hansen P.E., Duus F., Neumann R., Wesołowska A., Sośnicki J.G. and Jagodziński T.S.
Impedance Study of the Oxygen Evolution on the IrO2/TiO2/CeO2 System in Acidic Medium
- Alves V.A., da Silva L.A. and Boodts J.F.C.
Influence of Alkali Metal Chlorides on the Rate of Mutarotation of N-(p-Chlorophenyl)-b-D-glucopyranosylamine in Methanol
- Smiataczowa K. and Maj K.
Interaction of Ethanol with Alumina, Silica-Alumina and Zeolites
- Sarbak Z.
291-391
Reactivity of cis-Diaminedichloroplatinum(II)
(cis-Platin) Towards Chromium(VI)
by J. Stawińska1, Z. Staszak2, J. Jezierska3,
M. Cieślak-Golonka1 and M.
Daszkiewicz1
1Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Wrocław
University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland
2Institute
of Informatics and Management, Wrocław University of Technology,
Wybrzeże
Wyspiańskiego 27, 50-370 Wrocław, Poland
3Institute of Chemistry, University
of Wrocław, F. Joliot-Curie 14, 50-370 Wrocław, Poland
(Received July 21st, 1999; revised manuscript September 9th, 1999)
The interaction of Cr(VI) compounds: K2Cr2O7 and KCrO3Cl with cis-diaminedichloroplatinum(II) (cis-platin) has been studied spectroscopically (UV-VIS, IR, FIR, ESR). It was found that the redox processes took place with the precipitation of brown Pt(IV)-Cr(III) heteropolynuclear products. The deconvolution of the electronic spectra allowed the analysis in convention of independent Pt(IV) and Cr(III) crystal fields.
303-309
New Complexes of Samarium(III), Terbium(III)
and Holmium(III) with Quercetin-5'-sulfonic
Acid
by M. Kopacz and D. Nowak
Department of Inorganic and Analytical Chemistry, Chemical Faculty, University
of Technology,
35-959 Rzeszów, Poland e-mail:mkopacz@prz.rzeszow.pl
(Received July 21st, 1999; revised manuscript October 8th, 1999)
New solid complexes of samarium(III), terbium(III) and holmium(III) ions with quercetin-5'-sulfonic acid were obtained. Their composition and physicochemical properties were investigated. Ultraviolet, visible and infrared spectroscopy methods were used to determine the structure.
311-319
Large Scale Structures in Multicellular
Chemical Systems
by J. Maselko
Department of Chemistry, University of Alaska, Anchorage, AK 99508, USA
(Received July 21st, 1999; revised manuscript October 18th, 1999)
Calculations have led to the discovery of very complex, highly organized and beautiful structures. These structures develop from a single perturbation in a 2-D array of chemical cells. The chemistry in every cell is described by the Gray-Scott model, where cells are coupled by the diffusion of both chemical species. Many of the observed features were never seen in continuous media and may only occur in multicellular chemical systems. Some complex structures are bounded in space, while others are formed close to system boundaries. The characteristic properties are the growth of branches, subbranches, and the formation of closed compartments. The influence of symmetry of chemical medium and symmetry of initial perturbations on developed structures is also investigated.
321-330
Application of the Kamlet-Taft and Abraham Models
in Chemistry of Coordination
Compounds in the Solutions
by W. Apostoluk, T. Tłaczała and L.L. Duda
Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland
(Received July 21st, 1999; revised manuscript October 29th, 1999)
Some aspects of solvent and solute effects in the chemistry of coordination compounds solutions have been considered in terms of the Kamlet-Taft and Abraham models.
|
331-347
Spectrochemical Properties of Noncubic Transition Metal
Complexes in Solution.
XI. Angular Overlap Studies of
Bis(oxalato)- and Bis(malonato)diaquachromate(III)
Complexes
in Aqueous Solution
by K. Kurzak
Department of Chemistry, University of Podlasie, PL 08-110 Siedlce, Poland
(Received July 21st, 1999; revised manuscript December 1st, 1999)
Mixed ligands chromium(III) complexes with monodentate (water) and bidentate ligands: oxalic acid deprotonated (ox -, oxalate ion) or malonic acid (mal -, malonate ion), have been synthesized, investigated and characterized structurally and spectroscopically. Their geometrical isomers: cis- and trans-, have been studied spectrophotometrically in aqueous solution. The poor experimental contours were resolved into the component bands by Gaussian analysis. The spectra were interpreted using D2h and C2v symmetry for trans- and cis- isomer, respectively. The resolved spectra have been treated using an angular overlap model (AOM). The effect of s- and p-bonding of the bidentate ligands upon the chromium(III) ion in aqueous solution was described and discussed.
349-360
The Anodic Behavior of Silver in Concentrated
Chloride Solutions
by B. Kołodziej
Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Technical
University,
50-370 Wrocław, Poland
(Received August 5th, 1999; revised manuscript December 6th, 1999)
The processes on the silver electrode during its anodic polarization in
concentrated chloride solutions (1.55.0 M) are identified. The analysis
of the potentiodynamic E-I relationships showed, that the anodic polarization
depends on the concentration of Cl ions and runs through two steps (peaks
A and B). The first step peak A corresponds to: a) the irreversible electrode
reaction involving the adsorption of the reaction product AgCl in the
solution, in which concentration of Cl Ł 2 M and b) the reversible electrode
reaction involving the adsorption of the type species (n = 3, 4), when
the concentration of Cl ł 4 M. The second step peak B corresponds to:
a) the increase of the passive layer of AgCl showing high porosity and
a low ohmic resistance in the solution in which concentration of Cl
Ł 2 M and b) the anodic process, which follows the dissolution-precipitation
model, in which the electrochemical reaction of
formation precedes the
chemical precipitation of AgCl in the solution with Cl ł 4 M. On the
basis of experimental functions Ip = f(v1/2) and Ep = f(v1/2) the values
of specific conductivity for the passive layer of AgCl at 4 M and 5 M chloride
solutions were calculated and they equal to 3.25×103 W1 cm1 and 2.66×103
W1 cm1 respectively. The structure differences of the passive AgCl layer
forming in the chloride solutions have been shown by the microscope scanning
analysis.
361-368
Synthesis and Magnetic Properties of µ-Terephthalato Binuclear Chromium(III) Complexes
by Y.-T. Li1,2, X.-C. Zeng1 and C.-W. Yan2
1Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064,
P. R. China
2Department of Chemistry, Qufu Normal University, Qufu Shandong,
273165, P. R. China
(Received August 16th, 1999)
Four new terephthalato-bridged binuclear chromium(III) complexes of the
formula [Cr2(TPHA)L4](NO3)4, where L stands for 4,4'-dimethyl-2,2'-bipyridine
(Me2bpy); 2,9-dimethyl-1,10-phenanthroline (Me2phen); 5-bromo-1,10-phenanthroline
(Br-phen) and 5-chloro-1,10-phenanthroline (Cl-phen), respectively, and
TPHA represents the terephthalate dianion, have been synthesized and characterized.
Based on the elemental analyses, molar conductance and magnetic moments
of room-temperature measurements, and spectroscopic studies, extended TPHA-bridged
structures consisting of two chromium(III) ions, each in an octahedral
environment are proposed for these complexes. The [Cr2(TPHA)(Me2bpy)4](NO3)4
(1) and [Cr2(TPHA)(Me2phen)4](NO3)4 (2) complexes were characterized by
variable temperature magnetic susceptibility (4~300 K) measurements and
the observed data were successfully simulated by the equation based on
the spin Hamiltonian operator, , giving the exchange integrals J = 2.98
cm1 for (1) and J = 3.15 cm1 for (2). This result indicates the presence
of a weak antiferromagnetic spin-exchange interaction between the metal
ions within each molecule.
|
369-376
Synthesis and Ferromagnetic Spin-Coupling in N,N'-Oxamidobis(benzoato)cuprate(II)
Bridged
Copper(II)Chromium(III) Heterobinuclear Complexes
by Y.-T. Li1,2, C.-W. Yan2 and X.-C. Zeng1
1Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064,
P. R. China
2Department of Chemistry, Qufu Normal University, Qufu Shandong,
273165, P. R. China
(Received August 25th, 1999)
Four new heterobinuclear complexes have been synthesized and characterized,
namely [Cu(obbz)Cr(L)2]NO3, where obbz denotes the oxamidobis(benzoato)
and L represents 2,2'-bipyridine (bpy); 1,10-phenanthroline (phen); 5-bromo-1,10-phenanthroline
(Br-phen) and 5-chloro-1,10-phenanthroline (Cl-phen). Based on the elemental
analyses, spectroscopic studies, magnetic moments (at room temperature)
and molar conductivity measurements, extended oxamido-bridged structures
consisting of a copper(II) and a chromium(III) ions, which have a square
planar environment and an octahedral environment, respectively, are proposed
for these complexes. The [Cu(obbz)Cr(bpy)2]NO3 (1) and [Cu(obbz)Cr(phen)2]NO3
(2) complexes have been further characterized by variable temperature
magnetic susceptibility (4.2~300 K) and the observed data were least-squares
fitted to the susceptibility equation derived from the spin Hamiltonian,
, giving the exchange integrals J = +27.5 cm1 for (1) and J = +26.2 cm1
for (2). These results are commensurate with ferromagnetic interactions
between adjacent metal ions within each molecule.
377-383
Synthesis, Characterization and Magnetism of Chloranilato-Bridged Chromium(III)Chromium(III) Binuclear Complexes
by Y.-T. Li1,2, C.-W. Yan2 and X.-C. Zeng1
1Department of Chemistry, Sichuan University, Chengdu, Sichuan, 610064,
P. R. China
2Department of Chemistry, Qufu Normal University, Qufu, Shandong,
273165, P. R. China
(Received September 3rd, 1999)
Four new chloranilato-bridged chromium(III)chromium(III) binuclear complexes
of the formula [Cr2(CA)L4](SO4)2 [L denotes 2,2'-bipyridine (bpy); 1,10-phenanthroline
(phen); 5-nitro-1,10-phenanthroline (NO2-phen) and 5-bromo-1,10-phenanthroline
(Br-phen), respectively], where CA represents the dianion of chloranilic
acid, have been synthesized and characterized. Based on elemental analyses,
molar conductivity and magnetic moment of room-temperature measurements
and spectroscopic studies, it is proposed that these complexes have CA-bridged
structures and consist of two chromium(III) ions, each in a distorted octahedral
environment. The complexes [Cr2(CA)(phen)4](SO4)2 (1) and [Cr2(CA)(bpy)4](SO4)2
(2) were further characterized by variable temperature (4~300 K) magnetic
susceptibility measurements and the observed data were successfully simulated
by the equation based on the spin Hamiltonian operator, , giving the exchange
parameter J = 8.9 cm1 for (1) and J = 6.6 cm1 for (2). This result
indicates that there is a weak antiferromagnetic spin-exchange interaction
between the two chromium(III) ions within each molecule.
385-392
Copper(I) Sulfamate p-Complexes:
Synthesis and Crystal Structure of [{(CH2=CHCH2)2NCHO}Cu(NH2SO3)(H2O)]
Compound
by Ya.E. Filinchuk, O.P. Melnyk and M.G. Myskiv
Department of Chemistry, Ivan Franko State University,
Kyryla and Mefodiya
Str. 6, 290005, Lviv, Ukraine
E-mail: margm@chem. franko.lviv.ua
(Received September 27th, 1999; revised manuscript November 29th, 1999)
By alternating-current electrochemical synthesis, the crystalline p-complex [{(CH2=CHCH2)2NCHO}Cu(NH2SO3)(H2O)] (I) has been obtained, using copper(II) sulfamate and diallylformamide (DAFA) in water-methanolic solution and copper-wire electrodes. The single crystal of the compound was X-ray structurally characterized. The Cu atom possesses trigonal pyramidal coordination, formed by nitrogen atom of sulfamate anion and two C=C bonds of the same DAFA molecule at the equatorial plane and the oxygen atom of H2O molecule at the apical position. Hydrogen contacts for the most part by (N)H...O and (Ow)H...O bonds of 1.98(3)2.24(2) o connect separate moieties of the mononuclear complex into a three-dimensional framework. The effective atomic charges in I are calculated.
|
393-408
The Influence of (O, N)-Deuteration on the Crystal
and Molecular Structure,
Thermal Stability and
Spectroscopic Properties of 1,3-Propanediammonium
Hydrogenphosphate Monohydrate
by E. Bartoszak-Adamska1, M. Figlerowicz2, M. Wiewiórowski2,
T. Gustafsson3,
I. Olovsson3 and M. Jaskólski1,2
1Department of Crystallography, Faculty of Chemistry, A. Mickiewicz University,
Grunwaldzka
6, 60-780 Poznań, Poland
2Institute of Bioorganic Chemistry, Polish Academy
of Sciences,
Noskowskiego 12/14, 61-704 Poznań, Poland
3Institute of Chemistry,
University of Uppsala Box 531, S-75121 Uppsala, Sweden
(Received October 18th, 1999)
Exchange of mobile hydrogen atoms in 1,3-propanediammonium hydrogenphosphate
for deuterium (OH®OD, NH®ND) affects the thermal stability of the salt.
Additionally, (O,N)-deuteration induces some unexpected changes in the
CH2- vibrations in the IR spectrum of this compound. The structure
of the title compound has been determined by single crystal X-ray diffraction
analysis at 290 K (protonated as well as deuterated crystals) and at 25
K (deuterated crystal). In all cases, the crystals are monoclinic, space
group, P21/c. For C3H12·HP
·H2O at 290 K (I) a = 7.0030(3), b =
16.7611(7), c = 7.8417(4) A, b = 113.766(4)o, V = 842.34(7) A3; for
C3H6D6
·DP
·D2O at 290 K (II) a = 7.008(1), b = 16.786(3), c = 7.861(1)
A, b = 113.77(1)o, V = 846.3(2) A3; and at 25 K (III) a = 6.938(3),
b = 16.634(9), c = 7.893(3) A, b = 113.81(5)o, V = 833.4(7) A3. The 1,3-propanediammonium
dication has the extended all-trans conformation. The structure contains
a three-dimensional network of hydrogen bonds, in which all available
proton donors are engaged. The phosphate groups are linked through relatively
strong H bonds to form infinite chains along c. The water molecule is closely
associated with these chains by donating H bonds to two consecutive phosphate
units along the chain.
409-420
Deuterium Isotope Effects of o-Hydroxythioamides, 2-Thiazolines and 5-Acyl-2-thiobarbituric
Acids
by P.E. Hansen1, F. Duus1, R. Neumann1, A. Wesolowska2,
J.G. Sosnicki2 and
T.S. Jagodzinski2
1Department of Life Sciences and Chemistry, Roskilde University,
P.O. Box
260, DK-4000 Roskilde, Denmark
Fax +45 46743011; e-mail: poulerik@virgil.ruc.dk
2Institute
of Fundamental Chemistry, Technical University of Szczecin,
Aleja Piastow
42, 71065 Szczecin, Poland
(Received October 14th, 1999)
Deuterium isotope effects on 13C chemical shifts are studied in a series of o-hydroxythioamides, 2D-thiazolines and enolic 5-acyl-2-thiobarbituric acids. Novel 2-hydroxy-1-thiocarboxamide naphthalenes show steric isotope effects of opposite sign to those observed in 2-hydroxy-1-acetylnaphthalenes and pyrenes. The o-hydroxyaromatic 2D-thiazolines show tautomeric behaviour and accordingly large isotope effects. Tautomerism of these and the thioamides are discussed in relation to structure. Intramolecular hydrogen bonding of non-RAHB type show only weak effects. The enolic mono N-alkyl 5-acyl 2-thiobarbituric acids show two isomers, both of which are involved in enol-enol tautomerism.
421-428
Impedance Study of the Oxygen Evolution on the IrO2/TiO2/CeO2 System in Acidic Medium
by V.A. Alves1, L.A. da Silva2 and J.F.C. Boodts3
1Departamento de Química da FFCLRP, Universidade de Sao Paulo, Av. Bandeirantes,
3900
CEP 14040-901 Ribeirao Preto S.P. - Brasil
2Departamento de Morfologia
da FMRP, Universidade de Sao Paulo, Av. Bandeirantes, 3900
CEP 14049-900
Ribeirao Preto - S.P. - Brasil
3Departamento de Química, Universidade Federal
de Uberlândia, Av. Joao Naves de Ávila, s/n
CEP 38400-902 Uberlândia - M.G.
- Brasil
(Received June 28th, 1999; revised manuscript October 29th, 1999)
The oxygen evolution reaction has been studied for various Ti supported Ir0.3Ti(0.7-x)CexO2 anodes (0 Ł x Ł 0.7) by impedance measurements (EIS) at potentials between 0.4 and 1.6 V/rhe, in 1.0 mol dm3 HClO4. The electrical parameters of the oxide electrode solution interface were obtained by fitting the experimental impedance data to the RW(R1Q1)Qdl or RW(R1Q1)(RctQdl) equivalent circuits, depending on the potential. The ohmic resistance values, RW, situated between 0.6 and 1.3 W cm2, obtained from EIS are consistent with that obtained from the Tafel plots. The impedance spectrum in the cyclic voltammetry region (0.41.4 V) is an almost vertical line at the low frequency region, indicating the interfacial impedance is purely capacitive. The (R1Q1) combination is related to the film processes observed in the high frequency domain of the impedance spectra, independent of the potential and composition. The Qdl describes the double layer capacitance, Cdl, of the oxidesolution interface, which is seen to increase significantly with CeO2 introduction, as a result of the electrode electrochemical active surface area increase. The introduction of CeO2 in the IrO2/TiO2 binary system results in a decrease of the Rct values with respect to the oxygen evolution reaction, which is probably related to the active surface area increase of CeO2-containing anodes.
429-437
Influence of Alkali Metal Chlorides
on the Rate of Mutarotation of
N-(p-Chlorophenyl)-b-D-glucopyranosylamine
in
Methanol
by K. Smiataczowa and K. Maj
Faculty of Chemistry, University of Gdańsk, 80-952 Gdańsk, Sobieskiego 18, Poland
(Received September 20th, 1999; revised manuscript November 2nd, 1999)
The rate of benzoic acid catalyzed mutarotation reaction of N-(p-chlorophenyl)-b-D-glucopyranosylamine has been studied in the presence of LiCl, NaCl, KCl, RbCl, CsCl, NH4Cl and (CH3)4NCl in methanol and in methanolic benzoate buffer solutions, at 25oC. The effect of the ionic strength on the reaction, catalyzed by hydrogen ions and benzoic acid molecules, has been discussed. No specific interactions between the alkali metal ions and the reactant have been observed. Logarithms of the rate constants of the mutarotation reaction have been found to be linearly related to the dissociation constants of the alkali metal chlorides in methanol.
439-446
Interaction of Ethanol with Alumina,
Silica Alumina and Zeolites
by Z. Sarbak
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
(Received October 22nd, 1999; revised manuscript December 9th, 1999)
Fourier-transform infrared spectroscopy (FT-IR) has been applied to study the interaction of ethanol vapour with alumina (Degussa C), silica-alumina (Grace Division Chemical Research), zeolite X (Union Carbide) and zeolite ZMS-5 (laboratory made). Different surface species have been identified after heating at 35, 200 and 300oC. The interaction of ethanol with Al2O3 at 200oC results in formation of a carboxylate system, which at temperature higher than 200oC undergoes further decomposition with production of conventional (aromatic) coke and a species resembling acetyl groups. As a result of the interaction with amorphous silica-alumina, conventional coke is produced already at 200oC, while with HX zeolite a deposit of a mixture of conventional coke and carboxylate coke is formed. At 300oC, the carboxylic deposit substantially disappears. The interaction of ethanol vapours with H-ZSM-5 zeolite at 200 and 300oC leads to formation of a conventional deposit of alkyl-substituted naphthalenes and /or plyphenylenes. As a result of ethanol dehydration water molecules were also detected.
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