Acid Complexes with Some Metal Ions

Polish J. Chem., 77, 1059–1077 (2003) REVIEW ARTICLE

Equilibrium Study of Iminodi(methylenephosphonic) Acid Complexes with Some Metal Ions

by B. Kurzak and A. Kamecka

Institute of Chemistry, University of Podlasie, ul. 3 Maja 54, 08-110 Siedlce, Poland

(Received December 3rd, 2002; revised manuscript April 25th, 2003)

This article discusses coordination preferences of N-substituted iminodi(methylenephosphonic) acids to the different metal ions in an aqueous solution. These ligands exhibit high complexation efficiency towards divalent metal ions. This results from both dinegatively charged phosphonate groups as well as the imino nitrogen present in their structure. A significant preference for an equimolar stoichiometry has been demonstrated in these systems. The only exception is the N-2-methyltetrahydrofurylimino- di(methylenephosphonic) acid with a tetrahydrofuryl moiety, placed in the sterically favoured position that allows its oxygen atom to be an effective metal binding site. Spe- cific interactions between metal ions and furyl oxygen results in higher binding ability of this ligand and a formation of 1:2 species. Coordination properties of iminodi- (methylenephosphonic) acids are important factors to understand the role of the ligands and metal ions in biological systems. A summary presented in this review points on the direction of the research for future work in this area, which should be developed. Polish J. Chem., 77, 1079–1111 (2003) REVIEW ARTICLE

Resorcinarenes

by W. Œliwa, T. Zujewska and B. Bachowska

Institute of Chemistry and Environmental Protection, Pedagogical University, al. Armii Krajowej 13/15, 42-201 Czêstochowa, Poland (Received May 5th, 2003)

Selected examples of resorcinarenes are described, concerning their syntheses and reac- tivity. Formation of complexes, host-guest systems and capsules is also presented along with their possible applications. A short comment concerning pyrogalloarenes is added. In the paper references are cited of works that appeared during the years 1998–2003. Polish J. Chem., 77, 1113–1119 (2003) INORGANIC CHEMISTRY

Synthesis and Characterization of Mixed Phosphazene–Glycolate Complexes of Antimony(III)

by Y. Paul and S.K. Pandey

Department of Chemistry, University of Jammu, Baba Saheb Ambedkar Road, Jammu -180 006, (J & K), India (Received March 11th, 2003; revised manuscript April 28th, 2003)

Antimony(III)triazadiphosphorine complexes, [N(PPh2NR’)2SbOGO] (where R’ = -Ph or -SiMe3 and G = -CHMeCH2-, -CHMeCH2CMe2-, -CH2CH2CH2-, -CH2CMe2CH2-, -CH2CEt2CH2- or -CMe2CMe2-), have been synthesized by the reaction of bis-phenyl- ated acyclic phosphazene ligand, H[N(PPh2NPh)2], or bis-silylated acyclic phosphazene ligand, H[N(PPh2NSiMe3)2], with various cycloalkylenedioxyalkoxystibine, [OGOSb(OR)], (where R = -Et or -Pri) under anhydrous and inert conditions. The mixed phosphazene-glycolate derivatives of antimony(III) have been characterized by elemental analysis (C, H, N and Sb), molecular weight determination, mass, IR and NMR (1H, 13C and 31P) spectroscopies. The studies suggested a bidentate mode of bonding by phosphazene ligand that may lead to Y-trigonal bipyramidal coordination around the antimony. Ahydrolytically stable and rubber like material has been obtained on pyrolysis of [N(PPh2NPh)2SbOCH2CMe2CH2O] which, probably, has an oligomeric composition like {N(PPh2)2(NPh)2Sb}n . Polish J. Chem., 77, 1121–1129 (2003)

Synthesis, Spectroscopic Characteristics and Conductometric Investigation of New Tetrachloro- and Tetrabromoferrates(1-)

by Z. Warnke, D. Wyrzykowski and G. Wawrzyniak

Faculty of Chemistry, University of Gdañsk, 80-952 Gdañsk, Sobieskiego 18, Poland (Received March 11th, 2003; revised manuscript May 29th, 2003)

Synthetic pathways have been traced for new tetrachloro- and tetrabromoferrates(1-) of

empirical formulae [AH][FeX4], (AH)2FeBr5, (AH)3Fe2Cl9 and (AH)4Fe2Cl10, where A stands for pyridine, quinoline and their derivatives, and X = Cl, Br. The spectroscopic ev- idence (IR, far-IR, Raman and UV-Vis) has shown that the Fe − ions preserve their tetra X4 - hedral structure and that the nitrogen atom in the rings of pyridine and quinoline is protonated. On the basis of conductometric measurements relative stabilities of the an- ions were estimated in methanol (MeOH), dimethyl sulfoxide (DMSO) and dichloro-

methane (CH2Cl2), representing both polar (amphiprotic and protic) and non-polar solvents. Dissociation constants of the compounds were calculated based on the ex- panded Pitt’s equation. Results of the conductometric measurements have been sup- ported by electronic spectra. Polish J. Chem., 77, 1131–1134 (2003)

Study of Phase Equilibria in the System Nd2O3–Na2O–P2O5. The Quasi-Binary Section Nd(PO3)3–NaPO3

by T. Znamierowska and Sz. Bandrowski

Department of Inorganic Chemistry, Faculty of Engineering and Economics, Wroc³aw University of Economics, Komandorska 118/120, 53-345 Wroc³aw, Poland (Received May 29th, 2003; revised manuscript July 1st, 2003)

The quasi-binary section Nd(PO3)3–NaPO3 has been investigated by thermoanalytical methods (DTA, TG, DTG) and X-ray powder diffraction and its phase diagram was pro- posed. It was found that initial metaphosphates react at a 1:1 molar ratio, forming the in- termediate compound NaNd(PO3)4. It was confirmed, that it melts incongruently at about 866°C, giving Nd(PO3)3 and a liquid rich in NaPO3. The phosphate NaNd(PO3)4 is stable to room temperature and does not exhibit polymorphic transitions. Polish J. Chem., 77, 1135–1140 (2003) ORGANIC CHEMISTRY

Structure of the Polysaccharide O-Antigen of Salmonella Aberdeen (O : 11)

by J. Szafranek1, M. Kaczyñska1, Z. Kaczyñski1, J. Gajdus1, M. Czerwicka1, H. Dziadziuszko2 and R. G³oœnicka2

1Faculty of Chemistry, University of Gdañsk, 80-952 Gdañsk, Sobieskiego 18, Poland 2Institute of Maritime and Tropical Medicine, 81-519 Gdynia, Powstania Styczniowego 9b, Poland

(Received February 24th, 2003; revised manuscript June 9th, 2003)

O-specific polysaccharide (OPS) of Salmonella Aberdeen was obtained from bacterial cell mass by water-phenol extraction procedure of lipopolysaccharide (LPS) followed by its mild acid hydrolysis and gel filtration of soluble carbohydrate material. Rhamnose, galactose, N-acetyl-glucosamine and mannose were detected and their linkages were established. Sugar configurations, D or L, were determined for (S)-(+)-2-butyl glycosides on an achiral capillary column. The structure of OPS was determined by analysis of spectra of 1H and 13C NMR and homonuclear and heteronuclear correlations spectra. Anomeric configurations were tentatively assigned by chromium trioxide oxidation and later proved by anomeric proton chemical shifts, H1-H2 coupling constants and proton coupled 13C spectra. Sugar sequences were established from comparisons of specific carbon shifts with those from literature, two-dimensional nuclear Overhauser effect spectroscopy (NOESY) and heteronuclear multiple-bond correlation experiments (HMBC). The repeating unit of S. Aberdeen OPS has the structure: ®3)-b-D-GlcpNAc-(1®3)-[ b-D-Manp-(1®4)-]a-D-Galp-(1®4)-a-L-Rhap-(1® Polish J. Chem., 77, 1141–1147 (2003)

A Facile Synthesis of 4-Aryl-1H-pyrazolo[3,4-b]quinolines

by K. Chaczatrian, G. Chaczatrian, A. Danel and P. Tomasik

Department of Chemistry, University of Agriculture, Mickiewicz Ave. 21, 31-120 Cracow, Poland (Received April 24th, 2003; revised manuscript June 9th, 2003)

A novel synthesis of 1H-pyrazolo[3,4-b]quinolines, luminophores for electroluminescent devices, was developed. Conventional heating (180–190°C in ethylene glycol) or micro- wave exposure of a three-component mixture of an aromatic aldehyde, 3-substituted 1-phenyl-4,5-dihydro-1H-pyrazol-5-one and aromatic amine produced 4-aryl-1H-pyrazolo[3,4-b]quinolines. Polish J. Chem., 77, 1149–1155 (2003)

A Facile Synthesis of Annulated 2,2¢-Bipyridine Ligands with Alkylsulfanyl and Alkylsulfonyl Substituents in the 6 and 6’ Positions [1]

by D. Branowska and J. Kielak

Department of Chemistry, University of Podlasie, 3-go Maja 54, 08-110 Siedlce, Poland

(Received June 6th, 2003; revised manuscript June 17th, 2003)

3,3¢-Bis(isopropylsulfanyl)-5,5¢-bi-1,2,4-triazine 2 is easily transformed into annulated 2,2¢-bipyridines 4 and 6 with fused cycloalkene rings via [4+2]cycloaddition/retro cycloaddition reaction with cyclic enamines 3a–d. Oxidation of 4 and 6 with potassium permanganate under phase transfer catalysis conditions provided a series of the corresponding sulfonyl derivatives 7 and 8. Polish J. Chem., 77, 1157–1161 (2003)

Aromatic Nucleophilic Substitution in 1,2,4-Triazine 4-Oxides with Grignard Reagents

by A.M. Prokhorov, D.N. Kozhevnikov, V.L. Rusinov and O.N. Chupakhin

Urals State Technical University, 620002, Ekaterinburg, Russian Federation Fax: +7 3432 740458, E-mail: [email protected] (Received July 8th, 2003)

Addition of the Grignard reagents to 1,2,4-triazine 4-oxides followed by aromatization of the intermediatesH-adducts by dehydrogenation or dehydration was used for synthesis of 5-alkyl- or 5-aryl-substituted 1,2,4-triazines and their 4-oxides. Polish J. Chem., 77, 1163–1173 (2003) PHYSICAL CHEMISTRY

Sweetness-Vibrational Spectra Relationship in Aldopyranoses and Sucrose/Galactosucrose System

by W. Pietrzycki

Department of Chemistry, H. Ko³³¹taj University of Agriculture, Mickiewicz Avenue 21, 31-120 Kraków, Poland (Received January 29th, 2003; revised manuscript May 14th, 2003)

Correlation of the RS relative sweetnesses of 6 aldopyranoses, maltose and lactose on the structures of their PM3 vibrational spectra are analysed. The QSAR correlations of log(RS) versus squares of n(OH) stretching, d(COH) bending and T(OC) torsion calculated frequencies are examined. High correlations are found for n2(4-OH), d2(4-COH) and T2(4-OC) parameters, so the corresponding vibrations are called “sweet vibrations”. Computational QSAR procedure with two n2(O–H) vibrational parameters is applied to localize AH,B Shallenberger glycophore. The high correlation reached by author for n(4-OH) and n(3-OH) frequencies makes agree 4-OH, O-3 structure with AH,B glycophore. It allows to recover B = O-3 subsite, which is inactive in aldopyranoses due to electrostatic model. Analysis of the PM3 vibrational spectra of sucrose, galactosucrose and their chlorodeoxy derivatives is carried out. Based on QSAR procedure with four n2(O–H) vibrational parameters one can define Nofre-Tinti four-subsite sweetener in sucrose and galactosucrose molecules. Computations indicate for contribution of 4-OH, 3-OH pyranose groups and 1’-OH, 6’-OH fructofuranose groups. It speaks well for XH1, B2, E1, E4 sweetener in the sucrose/galactosucrose structure. Polish J. Chem., 77, 1175–1184 (2003)

Study of Complex Formation of n-Alkylammonium Cations by Dibenzo-18-crown-6, Dibenzo-21-crown-7, and Dibenzo-24-crown-8 in Acetonitrile, Nitromethane and Nitrobenzene Solvents and Their Binary Mixtures Using Conductometric Method

by S. Sadeghi and M.Sh. Valavi

Department of Chemistry, Faculty of Science, Birjand University, Birjand, Iran

(Received June 24th, 2002; revised manuscript May 20th, 2003)

The complex formation of ammonium and four n-alkylammonium perchlorate salts with dibenzo-18-crown-6 (DB18C6), dibenzo-21-crown-7 (DB21C7) and dibenzo-24-crown-8 (DB24C8) was studied by conductometry in acetonitrile (AN), nitrobenzene (NB) and nitromethane (NM) solvents at different temperatures and their binary mixtures at 25°C. The stability constants of the resulting 1:1 complexes were determined and found to de- crease in the order: DB21C7 > DB18C6 > DB24C8. Number of hydrogen atoms on the ammonium group available for bonding to the crown ethers was the most important fac- tor in determining complex stability constant.The influence of other factors such as the + size of the macrocyclic cavity, steric effect of the alkyl group attached to the −NH3 group, and the Gutmann donicity of the solvents on stability of the complexes were studied. In all cases, the stability constants of the resulted complexes in solvents used varied in the order: NB > NM > AN. Standard enthalpies and entropies of the complex formation were obtained from the temperature dependence of the stability constants. Obtained thermo- dynamic parameters were sensitive to the type of solvent. The enthalpy – entropy com- pensation effect was investigated in general complexation of cations with crown ethers. Polish J. Chem., 77, 1185–1190 (2003)

Activity Coefficient Behaviour of Nonelectrolytes in Sulfuric Acid Solutions

by H. Vanjari and R. Pande

School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur (C.G.), 492 010, India

(Received February 26th, 2003; revised manuscript May 30th, 2003)

Activity coefficient behaviour of ten nonelectrolytes in sulfuric acid solutions have been investigated by evaluating their distribution ratios as a function of electrolyte concentra- tions. Their salting-in parameters and values of Setschenow constant are also reported to understand the structure-activity relationship. Polish J. Chem., 77, 1191–1198 (2003)

Influence of Active Carbon Modification on Its Porous Structure and Heat Effects of Methanol Vapours Adsorption

by B. Buczek and L. Czepirski

AGH University of Science and Technology, Faculty of Fuels and Energy, Al. Mickiewicza 30, 30-059 Cracow, Poland (Received April 16th, 2003; revised manuscript June 11th, 2003)

Methanol adsorption of the active carbon seems to be very interesting for use in thermo- dynamic systems such as heat pumps and transformers as well as cooling systems. The porous structure of commercial active carbon modified by successive removal of exter- nal layers from a particle surface as produced by abrasion in a spouted bed and by demin- eralization was evaluated on the basis of the nitrogen adsorption data and those for methanol. The modifications improve densimetric characteristics and heat effects of methanol adsorption. Porous structure parameters obtained for nitrogen and methanol agreed reasonably well and Dubinin-Radushkevich approach can be a useful method for characterization of these systems. The methods for calculation of heat effects of methanol adsorption in a wide range of temperature and pressures are discussed. Polish J. Chem., 77, 1199–1206 (2003)

Passivation of Silver and Current Oscillations During + Anodic Dissolution of Silver in H2SO4 +Ag Solutions

by M. Dolata and P. Kêdzierzawski

Institute of Physical Chemistry Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland E-mail: [email protected], [email protected] (Received May 28th, 2003; revised manuscript June 16th, 2003)

We report the first observation of silver electrode passivation during anodic dissolution in sulphuric acid electrolytes. The passivation is of a salt type. Preliminary observations of nonlinear effects in this system: current oscillations and multiperiodic cyclic voltam- mograms are also presented. Microscopic inspection revealed, that during dissolution of the electrode, silver powder accumulates at the surface. Observed oscillations have a strong transient character, presumably resulting from the modification of diffusion conditions by powder accumulation. Polish J. Chem., 77, 1207–1212 (2003)

Free Energy of Hydride Formation in Pd-Ni Alloys System

by B. Baranowski and L. Dêbowska

Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

(Received June 18th, 2003)

Formation and decomposition pressures of hydrides for Ni0.3Pd0.7,Ni0.5Pd0.5,Ni0.7Pd0.3 and Ni0.9Pd0.1 alloys have been determined by following the thermoelectric power of these alloys as function of hydrogen pressure at 298 K. From the desorption pressures the free energies of hydride formation were calculated. These results combined with literature data are discussed in terms of deviation from an ideal behavior. The dominance of nickel is clearly demonstrated, what could be expected from its large hydride formation pressure in comparison with palladium hydride. The term “excess free energy of formation” is introduced and discussed for the alloy system treated. Polish J. Chem., 77, 1213–1216 (2003) DISCUSSION

The Nature of Phase Transitions in Me–H Systems. Coherent and Incoherent Equilibria

by B. Baranowski and L. Dêbowska

Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Kasprzaka 44/52, Poland

(Received June 25th, 2003) Polish J. Chem., 77, 1217–1220 (2003) COMMUNICATION

Concomitant Rearrangement of 15 [ N-NO2]-N-(4-Fluorophenyl)-N-methylnitramine and N-Methyl-N-phenylnitramine

by Z. Daszkiewicz and J.B. Kyzio³

Institute of Chemistry, University of Opole, 45-052 Opole, ul. Oleska 48, Poland

(Received June 6th, 2003)