POLISH JOURNAL OF CHEMISTRY
Volume 74 Number 3 March 2000
Pages 291-446

INORGANIC CHEMISTRY

291

Reactivity of cis-Diaminedichloroplatinum(II) (cis-Platin) Towards Chromium(VI)

- Stawińska J., Staszak Z., Jezierska J., Cieślak-Golonka M. and Daszkiewicz M.

303

New Complexes of Samarium(III), Terbium(III) and Holmium(III) with Quercetin-5'-sulfonic Acid

- Kopacz M. and Nowak D.

311

Large Scale Structures in Multicellular Chemical Systems

- Masełko J.

321

Application of the Kamlet-Taft and Abraham Models in Chemistry of Coordination Compound in the Solutions

- Apostoluk W., Tłaczała T. and Duda L.L.

331

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.

349

The Anodic Behavior of Silver in Concentrated Chloride Solutions

- Kołodziej B.

361

Synthesis and Magnetic Properties of m-Terephthalato Binuclear Chromium(III) Complexes

- Li Y.T., Zeng X.C. and Yan C.W.

369

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.

377

Synthesis, Characterization and Magnetism of Chloranilato-Bridged Chromium(III)Chromium(III) Binuclear Complexes

- Li Y.T., Yan C.W. and Zeng X.C.

385

Copper(I) Sulfamate p-Complexes: Synthesis and Crystal Structure of [{(CH₂=CHCH₂-)₂N-CHO}Cu(NH₂SO₃)(H₂O)] Compound

- Filinchuk Ya.E., Mel’nyk O.P. and Mys’kiv M.G.

PHYSICAL CHEMISTRY

393

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.

409

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.

421

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.

429

Influence of Alkali Metal Chlorides on the Rate of Mutarotation of N-(p-Chlorophenyl)-b-D-glucopyranosylamine in Methanol

- Smiataczowa K. and Maj K.

439

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 D_2h and C_2v 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 (1.5–5.0 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 I_p = f(v^1/2) and E_p = f(v^1/2) 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 3.25×10^–3 W^–1 cm^–1 and 2.66×10^–3 W^–1 cm^–1 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. Li^1,2, 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 cm^–1 for (1) and J = –3.15 cm^–1 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. Li^1,2, 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 cm^–1 for (1) and J = +26.2 cm^–1 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. Li^1,2, 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 cm^–1 for (1) and J = –6.6 cm^–1 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–)₂N–CHO}Cu(NH₂SO₃)(H₂O)] Compound

by Ya.E. Filinchuk, O.P. Mel’nyk and M.G. Mys’kiv

Department of Chemistry, Ivan Franko State University,
Kyryla and Mefodiya Str. 6, 290005, L’viv, 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–)₂N–CHO}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 (O_w)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. Jaskólski^1,2

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 Ir_0.3Ti_(0.7-x)Ce_xO₂ 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 dm^–3 HClO₄. The electrical parameters of the oxide electrode solution interface were obtained by fitting the experimental impedance data to the R_W(R₁Q₁)Q_dl or R_W(R₁Q₁)(R_ctQ_dl) equivalent circuits, depending on the potential. The ohmic resistance values, R_W, 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 (0.4–1.4 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 Q_dl describes the double layer capacitance, C_dl, of the oxide–solution 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 R_ct 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 25^oC. 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 300^oC. The interaction of ethanol with Al₂O₃ at 200^oC results in formation of a carboxylate system, which at temperature higher than 200^oC  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 200^oC, while with HX zeolite a deposit of a mixture of conventional coke and carboxylate coke is formed. At 300^oC, the carboxylic deposit substantially disappears. The interaction of ethanol vapours with H-ZSM-5 zeolite at 200 and 300^oC 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.