POLISH JOURNAL OF CHEMISTRY
Volume 72 Number 3 March 1998
Pages 485- 654


CONTENTS

Page

INORGANIC CHEMISTRY
485 Synthesis and Magnetism of Heterobinuclear Cu(II)-Fe(II) Complexes Bridged by N,N'-
-Bis(3-aminopropyl)oxamidocopper(II)

— Li Y.T., Yan C.W., Zhu X.D. and Liao D.Z.
492 Studies of Au(I) Complexes with Perfluorinated Carboxylates and Trimethylphosphine
— Lakomska I., Grodzicki A. and Szlyk E.
498 Synthesis, Properties and Thermal Decomposition of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Succinates
— Brzyska W. and Galkowska B.
504 Mass Spectrometric Behaviour of Alkali and Alkaline Earths Acetylacetonates
— Plaziak A.S., Urbaniak W., Franski R. and Gierczyk B.
511 Interactions between the Components in the Zr-Cu-In System at 870 K
— Gulay L.D., Zaremba V.I., Kalychak Ya.M., Stepien-Damm J. and Kobluck N.O.
514 The Structure and Properties of a Palladium(II) Complex of 2-Mercapto-1-methylimidazole
— Wisniewski M.Z. and Glowiak T.
519 Synthesis and Spectral Characterization of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) Complexes Produced from the Template Reaction of Diacetyloxime and 1,2-Diaminopropane
— El-Tabl A.S. and Kashar T.I.
ORGANIC CHEMISTRY
527 Effects of Molecular Association on the NMR Shielding Constant in Methylamine
— Jackowski K., Les A. and Bernatowicz P.
534 Synthesis of Novel Phosphocane Incorporating a Selenium Atom in the Cycle
— Li J.L., Tian B., Zhao C.Q., Wang Y.M., Matsuura T. and Meng J.B.
537 Reactions of 4-Phosphoranylidene-5(4H)-oxazolones with Acylating Agents
—Mazurkiewicz R. and Grymel M.
548 Proinsulin C-peptides from Bovine, Ovine and Bisontine Pancreata
— Izdebski J., Fiertek D. and Majewski T.
554 Fragmentation of 1-Methyl-1,2,3,4-tetrahydroquinoline-2,3-dicarboxylic Acid Derivatives Upon Electron Ionization
— Danikiewicz W. and Wojciechowski K.
564 Synthesis of P-Chiral, Non-Racemic Phosphinylacetates via Enzymatic Resolution of Racemates
— Kielbasinski P., Zurawinski R., Pietrusiewicz K.M., Zablocka M. and Mikolajczyk M.
PHYSICAL CHEMISTRY
573 Studies on Kinetics and Mechanism of Oxidation of Pyridoxal by Dichromates in Aqueous HClO4 Solutions
— Kita E., Kita P., Pietkiewicz A., Wrzeszcz G. and Rozploch F.
582 Cooxidation of S-Phenylmercaptoacetic Acid and Oxalic Acid with Pyridinium Chlorochromate
— Mangalam G. and Subbiah Meenakshisundaram
587 Basicity of N-Arylglucopyranosylamines in Methanol
— Smiataczowa K., Maj K., Widernik T. and Nesterowicz M.
595 Preparation of cis-[Cr(N3)(bpy)2(H2O)]2+ Complex and Studies on a Composite Mechanism of Its Aquation Stimulated by Cr(aq)2+-Ions
— Katafias A., Kita P. and Madej E.
607 Reduction of NO Using Mn4+ and Fe3+-Impregnated Active Carbon
— Grzybek T. and Buczek B.
613 The Chemical States of Phosphorus on the Iron Surface
— Narkiewicz U.
618 Deuterium Isotope Fractionation between Ortho-alkyl Substituted Phenols and t-Butylthiol in Oxygen Bases
— Wawer A., Jelinska-Kazimierczuk M. and Szydlowski J.
CRYSTAL AND MOLECULAR STRUCTURES
627 Polymeric Crystal Structure of Trisaquo(µ-pyrazine-2,3-dicarboxylato)strontium(II)
— Ptasiewicz-Bak H. and Leciejewicz J.
633 Crystal, Molecular and Electronic Structure of [ReBr3(NO)(MeCN)(PPh3)] Complex
— Bartczak T.J., Czurak W., Dziegielewski J.O. and Machura B.
COMMUNICATIONS
643 Synthesis and Magnetism of µ-3-Nitro-phthalato-manganese(II) and Nickel (II) Binuclear Complexes
— Shi J.M., Cui J.Z., Liao D.Z., Miao M.M., Liu Y.J., Jiang Z.H. and Wang G.L.
647 Synthesis and Characterization of Complexes of 2,6-Pyridinedicarboxylic Tetra (Ethylene Glycol) Diester with Alkali and Alkaline Earth Nitrates
— Xue Q.S., Cheng P., Cui J.Z. and Wang G.L.
650 Stability of Valinomycin-Thallium Complex in Nitrobenzene Saturated with Water
— Makrlik E. and Vanura P.
BOOK REVIEW
654 John Emsley: CHEMIA - PRZEWODNIK PO PIERWIASTKACH, PWN, Warszawa, 1997, pp. 255 (in Polish), (translated from the II English edition: Oxford Chemistry Guides: The Elements, Clarendon Press, Oxford, 1991)
— Baranowski B.


ABSTRACTS


485-491

Synthesis and Magnetism of Heterobinuclear
Cu(II)-Fe(II) Complexes Bridged by N,N'-Bis(3-
aminopropyl)oxamidocopper(II)

by Y.T. Li1, C.W. Yan2, X.D. Zhu1 and D.Z. Liao3
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, Nankai University, Tianjin, 300071, P.R. China

(Received August 11th, 1997)

Four new µ-oxamido heterobinuclear complexes have been synthesized and characterized, namely [Cu(oxpn)Fe(L)2]SO4, where oxpn denotes the N,N'-bis(3-aminopropyl)oxamidodianion and L represents 1,10-phenanthroline(phen);5-nitro-1,10-phe- nanthroline (NO2-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 2,2'-bipyridine (bpy). 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 an iron(II) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. The [Cu(oxpn)Fe(bpy)2]SO4 (1) and [Cu(oxpn)Fe(phen)2]SO4 (2) complexes have been 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 including single-ion zero-field interaction for the iron(II) ion, H = -2J S 1S2-D Sz2, giving the exchange integrals J = -21.8 cm-1 for (1) and J = -23.2 cm-1 for (2). These results are commensurate with antiferromagnetic interactions between adjacent metal ions within each molecule.

492-497

Studies of Au(I) Complexes with Perfluorinated
Carboxylates and Trimethylphosphine

by I. Lakomska, A. Grodzicki and E. Szlyk
Nicolaus Copernicus University, Department of Chemistry, 87 100 Torun, Poland

(Received June 16th, 1997; revised manuscript September 8th, 1997)

Au(I) complexes of the type RCOOAuL, where R = C6F13, C7F15, C8F17, C9F19, C6F5, OOC(C3F6) and L - trimethylphosphine (Me3P) were synthesized and characterized by spectroscopic (IR, 13C, 19F, 31P NMR) and thermal methods. Spectroscopic results favour two coordinated Au(I) with unidentate bonded trimethylphosphine and carboxylates, whereas in the case of hexafluoroglutarate a dimeric structure has been found. The mode of carboxylates binding was proposed basing on the chemical shift of COO group in 13C NMR spectra and splitting of COO asymmetric and symmetric vibrations bands. Thermal decomposition proceeds in a multistage way that results in metallic gold. Decomposition temperatures and thermal stability of the studied complexes depend on the length of the perfluorinated chain.

498-503

Synthesis, Properties and Thermal Decomposition of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Succinates

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

(Received July 14th, 1997; revised manuscript October 1st, 1997)

Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) succinates were prepared as solids with general formula MC4H4O4.nH2O, where n = 3 for M = Ni, Co, n = 2 for M = Cd and n = 0 for M = Cu, Zn. IR spectra and X-ray diffractograms were recorded and solubilities in water and thermal decomposition in static air were investigated. During heating the hydrated complexes of Co(II)), Ni(II) and Cd(II) lose all water molecules in one step. All anhydrous complexes decompose to oxides MO with intermediate formation of free metals (Ni, Co, Cu) or oxocarbonates (Zn, Cd).

504-510

Mass Spectrometric Behaviour of Alkali and
Alkaline Earths Acetylacetonates

by A.S. Plaziak1,2, W. Urbaniak1, R. Franski2 and B. Gierczyk1
1Faculty of Chemistry and 2Instrumental Laboratory,
Adam Mickiewicz University, 60-780 Poznan, Poland
E-mail: plaziak@vm.amu.edu.pl

(Received September 5th, 1997; revised manuscript October 2nd, 1997)

EI spectra of acetylacetone, alkali acetylacetonates and acetylacetonates of alkaline earths of formulae M(I)(acac) and M(II)(acac)2 (where M(I) = Li, Na, K, Rb, Cs, M(II) = Be, Mg, Ca, Sr, acac = acetylacetonate ligand) were obtained using mass spectrometry. Ligand-ions were observed in each spectrum. Metal cations were present only for the elements of group I. The detection of polymeric species of general formula [Mx(acac)y]+ supports the conclusion, that polymeric species of acetylacetonates of group I and II are commonly present in the gas phase.

511-513

Interactions between the Components in the
Zr-Cu-In System at 870 K

by L.D. Gulay1, V.I. Zaremba1, Ya.M. Kalychak1,
J. Stepien-Damm2 and N.O. Kobluck1
1Inorganic Chemistry Department, Ivan Franko Lviv State University,
Kyryla and Mefodia 6, 290005 Lviv, Ukraine
2W. Trzebiatowski Institute of Low Temperature and Structure Research,
Polish Academy of Sciences, Okolna 2, 50-950 Wroclaw, Poland

(Received August 22nd, 1997; revised manuscript October 31st, 1997)

The interactions between components in Zr-Cu-In ternary system at 870 K have been studied by X-ray and microstructure analyses. One earlier known (ZrCu2In with MnCu2Al-type) and four unknown ternary compounds have been found. Crystal structure of all new compounds are determined: ZrCu5-xInx (x = 0.3-1.3) - AuBe5 type of structure (space group F43m, a = 6.955-7.042(2) ); ZrCuxIn3-x (x = 0.35-0.80) - AuCu3 type of structure (space group Pm 3m), a = 4.3281-4.3079(1) ); Zr2Cu2In - Mo2FeB2 type of structure (space group P4/mbm), a = 7.194(2) , c = 3.410(4) ; Zr5CuIn3 - Hf5CuSn3 structure type (space group P63/mcm, a = 8.671(2) , c = 5.917(1) ).

514-518

The Structure and Properties of a Palladium(II)
Complex of 2-Mercapto-1-methylimidazole

by M.Z. Wisniewski1 and T. Glowiak2
1Institute of Chemistry, Pedagogical University, 25-020 Kielce, ul. Checinska 5, Poland
2Institute of Chemistry, University of Wroclaw, 50-383 Wroclaw, Poland

(Received September 15th, 1997; revised manuscript November 3rd, 1997)

Complex of palladium(II) with 2-mercapto-1-methylimidazole has been prepared and studied by elemental analyses, X-ray diffraction, IR and far-IR spectroscopy and magnetic measurements. The crystal structure of the complex has been determined as follows: triclinic system, space group P1, a = 8.78(7) , b = 8.85(2) , c = 9.80(5) , = 66.7(5)o, ß = 86.9(5)o, = 72.0(1)o, V = 664.3 3.

519-526

Synthesis and Spectral Characterization of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) Complexes Produced from the Template Reaction of Diacetyloxime
and 1,2-Diaminopropane

by A.S. El-Tabl and T.I. Kashar
Department of Chemistry, Faculty of Science, Menoufia University, Shebin El- Kom, Egypt

(Received May 27th, 1997; revised manuscript November 12th, 1997)

A new series of Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes obtained by the template reaction of diacetyloxime and 1,2-diaminopropane with metal ions have been synthesized and characterized by elemental analyses, IR, VIS-UV, electrical conductivity, magnetic moment and ESR measurements. ESR spectrum of Cu(II) complex exhibits an axial type symmetry dx2-y2 with a covalent bond character. ESR spectrum of Ni(I) at 77 K formed by exposing the Ni(II) complex to ionizing radiation, points on dx2-y2 ground state. ESR spectrum of Fe(III) complex presents a low spin 57Fe(I = 1/2), d5, configuration with dz2 ground state.

527-533

Effects of Molecular Association on the NMR
Shielding Constants in Methylamine

by K. Jackowski, A. Les and P. Bernatowicz
Department of Chemistry, Warsaw University, ul. Pasteura 1, 02-093 Warszawa, Poland
E-mail: kjack@chem.uw.edu.pl

(Received September 19th, 1997)

The 15N, 13C and 1H NMR chemical shifts were measured for methylamine in the gaseous and liquid phase. The gas to liquid shifts reveal the deshielding effects for all investigated nuclei. It is shown that the hydrogen bonding is responsible for the largest changes, which are observed for the nitrogen and amino hydrogen atoms as well. The CHF-GIAO calculations indicate that the cyclic trimer of methylamine exhibits the shielding changes, which are in qualitative agreement with the gas to liquid shifts.

534-536

Synthesis of Novel Phosphocane Incorporating
a Selenium Atom in the Cycle

by J.L. Li, B. Tian, C.Q. Zhao, Y.M. Wang, T. Matsuura and J.B. Meng
Department of Chemistry, Nankai University, Tianjin 300071, P.R. China

(Received July 21st, 1997; revised manuscript October 3rd, 1997)

Six new 2-substituted-2-oxo-1,3,6,2-dioxaselenaphosphocanes were synthesized from bis(2-hydroethyl)selenide and alkyl or aryl phosphorodichloridates or phenylphosphonic dichloride.

537-547

Reactions of 4-Phosphoranylidene-5(4H)-oxazolones with Acylating Agents

by R. Mazurkiewicz and M. Grymel
Institute of Organic Chemistry and Technology, The Silesian Technical University,
ul. Krzywoustego 4, 44-100 Gliwice, Poland
E-mail: romanm@zeus.polsl.gliwice.pl (Received August 18th, 1997; revised manuscript October 13th, 1997)

Acyl iodides and bromides give in reaction with ylides 1 the expected 4-C- or O-acylation products 2 or 3. In contrast to acyl iodides and bromides, acyl chlorides give in reaction with the ylides 1 Wittig-like reaction products 4 (4-(1-chloroalkylidene)-5(4H)-oxazolones), whereas benzoyl fluoride gives 4-(1-benzoyloxybenzylidene)-5(4H)-oxazolones. Some evidence points to a mechanism of the formation of Wittig-like reaction products involving O-acylated ylides as intermediates.

548-553

Proinsulin C-peptides from Bovine, Ovine and Bisontine Pancreata

by J. Izdebski, D. Fiertek and T. Majewski
Laboratory of Peptides, Department of Chemistry, University of Warsaw,
PL-02093 Warsaw, Pasteura 1, Poland
E-mail: izdebski@chem.uw.edu.pl

(Received October 13th, 1997)

Two C-peptides corresponding to sequences of genetic variants of bovine proinsulin have been synthesized by solid-phase method. C-peptide containing material has been isolated from two bovine pancreata using acid-ethanol extraction, gel filtration on Sephadex G-50 and ion exchange chromatography on carboxymethyl cellulose. Comparison of these materials with synthetic standards on reverse-phase HPLC have revealed that both pancreata contained only one variant of C-peptide which had Pro in position 16. The second variant of bovine proinsulin C-peptide with Leu at this position has not been detected. The corresponding genetic variant of bovine proinsulin, containing Leu within C-peptide sequence, has been found by other authors in the material obtained from a pool of a large number of pancreata. Our results exclude the possibility that the two bovine proinsulins are a result of expression of two insulin genes in the bovine species as a whole. The same C-peptide was found in ovine and bisontine pancreata.

554-563

Fragmentation of 1-Methyl-1,2,3,4-tetrahydro-
quinoline-2,3-dicarboxylic Acid Derivatives
upon Electron Ionization

by W. Danikiewicz and K. Wojciechowski
Institute of Organic Chemistry, Polish Academy of Sciences,
ul. Kasprzaka 44/52, 01-224 Warszawa, Poland
E-mail: witold@ichf.edu.pl

(Received October 14th, 1997)

The electron ionization-induced fragmentation patterns of cis-3a,4,9,9a-tetrahydro-4-methyl-2-phenyl-1H-pyrrolo[3,4-b]quinoline-1,3(2H)-dione derivatives have been studied. It was found that fragmentation starts at the N-phenylsuccinimide ring and its pattern depends on the type and position of the substituents at carbon atoms 5-8. Peaks, which can be assigned to the products of the retro Diels-Alder opening of the nitrogen atom containing tetrahydroquinoline ring, were observed.

564-572

Synthesis of P-Chiral, Non-Racemic Phosphinylacetates via Enzymatic Resolution of Racemates

by P. Kielbasinski1, R. Zurawinski1, K.M. Pietrusiewicz2,
M. Zablocka1 and M. Mikolajczyk1
1Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
90-363 Lodz, Sienkiewicza 112, Poland
2Department of Chemistry, M. Curie-Sklodowska University, 20-031 Lublin, Poland

(Received October 10th, 1997; revised manuscript October 31st, 1997)

A series of racemic methyl phosphinylacetates was hydrolyzed in the presence of porcine liver esterase (PLE) under the kinetic resolution conditions to give the corresponding P-chiral phosphinylacetic acids and recovered esters in high enantiomeric purity (72-100% ee). The Jones' active site model was applied to explain the enantioselectivity of this reaction.

573-581

Studies on Kinetics and Mechanism of Oxidation of Pyridoxal by Dichromates in Aqueous HClO4 Solutions

by E. Kita, P. Kita, A. Pietkiewicz, G. Wrzeszcz and F. Rozploch
Faculty of Chemistry, N. Copernicus University, 87-100 Torun, Poland

(Received September 22nd, 1997)

Oxidation of pyridoxal (PL) by Cr2O72- ion has been studied using an excess of the aldehyde under air or argon atmospheres. The reaction leads mainly to two Cr(III) complexes: [Cr(PA)(H2O)4]2+ and [Cr(H2O)6]3+ and to uncoordinated pyridoxic acid (PA). The rate of PL oxidation follows a mixed third order rate law: first order in concentrations of Cr(VI), PL and H3O+. The reduction of Cr(VI) to Cr(III) proceeds through chromium(V) intermediate complex, which has been detected by the EPR method. Mechanism of the reaction has been discussed.

582-586

Cooxidation of S-Phenylmercaptoacetic Acid and Oxalic Acid with Pyridinium Chlorochromate

by G. Mangalam and Subbiah Meenakshisundaram
Department of Chemistry, Annamalai University, Annamalainagar - 608 002, India

(Received June 30th, 1997; revised manuscript October 2nd, 1997)

The kinetics of oxidation of the mixture of S-phenylmercaptoacetic acid (PMA) and oxalic acid with pyridinium chlorochromate (PCC) in 30% (v/v) acetic acid-water exhibits a first-order dependence each in [PCC] and [PMA], at low concentrations of the latter. At high concentration of the substrate, a fractional order in [PMA] is observed. The rate increases linearly with [oxalic acid]. Increased reactivity in the presence of oxalic acid with carbon dioxide as one of the products is well explained by Rocek's mechanism for cooxidation, involving a ternary complex. Formation of a ternary complex at low concentrations and decomposition of the complex at higher concentrat-
ions of PMA is considered to be the respective rate-limiting step.

587-594

Basicity of N-Arylglucopyranosylamines in Methanol

by K. Smiataczowa, K. Maj, T. Widernik and M. Nesterowicz
Faculty of Chemistry, University of Gdansk, 80-952 Gdansk, Poland

(Received July 28th, 1997; revised manuscript October 2nd, 1997)

Basicities of p-toluidine, m-toluidine, p-chloroaniline, m-chloroaniline and m-nitroaniline N-glucopyranosylamines have been determined by potentiometric titration in methanol at 25oC. The pKb values of successive N-glucosides have been derived from the Broensted relation, log k = f (pKb), using the rate constants of mutarotation, k. The same relationship served for the determination of basicities of several substituted anilines in methanol at 25oC. Basicity constants of the aniline derivatives and of the N-arylglucopyranosylamines in methanol have also been correlated with analogous constants of the compounds in water.

595-606

Preparation of cis-[Cr(N3)(bpy)2(H<->2O)]2+ Complex and Studies on a Composite Mechanism of Its Aquation Stimulated by Cr( aq )2+-Ions

by A. Katafias, P. Kita and E. Madej
Faculty of Chemistry, N. Copernicus University, 87-100 Torun, Poland

(Received August 4th, 1997; revised manuscript October 3rd, 1997)

Anation of cis-[Cr(bpy)2(H<->2O)2]3+ ion (bpy = 2,2'-bipyridine ) in HN3/N3- media gives a novel very inert monoazidocomplex whose formula and structure can be proposed as cis-[Cr(N3)(bpy)2(H2O)]2+. This complex decomposes rapidly by addition of Cr(aq)2+ into a deareated acidic solution. Analysis of the reaction products and the kinetics suggests an electron transfer Cr(II) -> Cr(III) via competitive reaction pathways: inner-sphere through Cr(III)-N3-Cr(II) intermediate, outer-sphere and/or perhaps also via a more direct interaction of Cr(II) with p-ring of the coordinated bipyridine.

607-612

Reduction of NO Using Mn4+ and
Fe3+ - Impregnated Active Carbon

by T. Grzybek and B. Buczek
Faculty of Fuels and Energy, University of Mining and Metallurgy,
Al. Mickiewicza 30, 30-059 Krakow, Poland

(Received October 6th, 1997)

Carbonaceous materials were promoted by consecutive impregnation with manganese salt (potassium permanganate with or without the addition of sulphuric acid) and iron salt. Texture of the materials obtained was studied by low temperature argon sorption and manganese and iron distribution by X-ray photoelectron spectroscopy. The influence of impregnating solution on the structure of the catalysts studied was discussed. Catalytic properties (activity and selectivity) in selective catalytic reduction of nitric oxide with ammonia of doubly promoted carbonaceous material were compared with iron or manganese-containing active carbon.

613-617

The Chemical States of Phosphorus
on the Iron Surface

by U. Narkiewicz
Technical University of Szczecin, Institute of Inorganic Technology,
Pulaskiego 10, 70-322 Szczecin, Poland
E-mail: un@mailbox.tuniv.szczecin.pl

(Received December 10th, 1996; revised manuscript October 10th, 1997)

The main purpose of this study was to investigate the segregation and oxidation of phosphorus on the polycrystalline iron surface using the AES and XPS methods. The segregation of phosphorus begins at 600 K and the maximum concentration of phosphorus on the surface is achieved at 720 K, as in the case of a monocrystalline sample. The segregation of sulphur begins above 720 K, whereas the phosphorus surface concentration decreases. The oxidation of the iron surface covered with phosphorus results in the formation of both the oxygen-phosphorus bonds and the oxygen-iron bonds. The different forms of surface species have been proposed.

618-626

Deuterium Isotope Fractionation between Ortho-alkyl Substituted Phenols and t-Butylthiol in Oxygen Bases

by A. Wawer, M. Jelinska-Kazimierczuk and J. Szydlowski
Chemistry Department, University of Warsaw, Zwirki i Wigury 101, 02-089 Warsaw, Poland
E-mail: jszydlow@chem.uw.edu.pl

(Received September 19th, 1997; revised manuscript October 17th, 1997)

Equilibrium isotope effect in the exchange reaction of deuterium between phenol (P), 2-isopropylphenol (IPP), 2,6-diisopropylphenol (DIPP), 2,6-ditertbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied at 298 K. The fractionation factors () have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulphoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that ln correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore it was found that in DTBT-TBT-base system ln depends linearly on the basicity of the solvent (DN parameters). On the other hand, ln correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition

627-632

Polymeric Crystal Structure of
Trisaquo(µ-pyrazine-2,3-dicarboxylato)strontium(II)

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

(Received August 28th, 1997; revised manuscript October 21st, 1997)

Trisaquo(µ-pyrazine-2,3-dicarboxylato)strontium(II), SrC6H8N2O7 crystals have been studied by X-ray diffraction. The strontium ion is coordinated by a heteroring nitrogen, Sr-N of 2.793 , and one oxygen atom belonging to a monodentate carboxylic group, Sr-O of 2.583 , situated close to this nitrogen atom. Two oxygen atoms of carboxylic groups belonging to adjacent complex molecules, Sr-O = 2.647 and 2.914 , bridge them into ribbons. Each oxygen atom of the above group is also linked to the Sr ions belonging to adjacent ribbons, Sr-O = 2.576 and 2.620 , forming molecular sheets, which are parallel to the (010) plane. Each Sr ion coordinates also three oxygen atoms of water molecules (the average distance is 2.669 . Hydrogen bonds of 2.66(1)-2.84 (1) link the sheets into a 3-dimensional framework.

633-642

Crystal, Molecular and Electronic Structure of [ReBr3(NO)(MeCN)(PPh3)] Complex

by T.J. Bartczak1, W. Czurak1, J.O. Dziegielewski2* and B. Machura2
1X-ray Crystallography Laboratory, Institute of General and Ecological Chemistry,
Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland
E-mail: tadekbar@ck-sg.p.lodz.pl
2Department of Inorganic and Radiation Chemistry, Institute of Chemistry,
University of Silesia, Szkolna 9, 40-006 Katowice, Poland

(Received September 22nd, 1997; revised manuscript November 7th, 1997)

A new rhenium nitrosyl complex has been synthesized and characterized by IR, UV-Vis, NMR (1H and 31P) and magnetochemical measurements. The crystal and molecular structure of [ReBr3(NO)(MeCN)(PPh3)] has been determined by X-rays. The Re atom is of six-coordinate distorted octahedral configuration and linear nitrosyl ligand is trans towards the acetonitrile molecule.

643-646

Synthesis and Magnetism of µ-3-Nitro-phthalato-
-manganese(II) and Nickel(II) Binuclear Complexes

by J.M. Shi1, J.Z. Cui1, D.Z. Liao1, M.M. Miao1, Y.J. Liu2,
Z.H. Jiang1 and G.L. Wang1
1Department of Chemistry, Nankai University, Tianjin 300071, P. R. China
2State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China

(Received July 16th, 1997; revised manuscript September 24th, 1997)

647-649

Synthesis and Characterization of Complexes of
2,6-Pyridinedicarboxylic Tetra (Ethylene Glycol)
Diester with Alkali and Alkaline Earth Nitrates

by Q.S. Xue1, P. Cheng2, J.Z. Cui2 and G.L. Wang2
1Tianjin Research Institute of Chemical Industry, Tianjin 300131, China
2Department of Chemistry, Nankai University, Tianjin 300071, China

(Received May 19th, 1997; revised manuscript October 28th, 1997)

650-653

Stability of Valinomycin-Thallium Complex in
Nitrobenzene Saturated with Water

by E. Makrlik1 and P. Vanura2
1Department of Chemistry, Charles University, Faculty of Education,
M.D. Rettigove 4, 116 39 Prague 1, Czech Republic
2Department of Analytical Chemistry, Prague Institute of Chemical Technology,
Technicka 5, 166 28 Prague 6, Czech Republic

(Received August 7th, 1997; revised manuscript November 6th, 1997)

654

John Emsley: CHEMIA - PRZEWODNIK PO PIERWIASTKACH,
PWN, Warszawa, 1997, pp. 255 (in Polish)
(translated from the II English edition: Oxford Chemistry Guides:
The Elements, Clarendon Press, Oxford, 1991)

(reviewed by B. Baranowski)


Return to main page.


© 1997 Polish Journal of Chemistry

prepared by (aws)