POLISH JOURNAL OF CHEMISTRY
Volume 72 Number 5 May 1998
Pages 815- 970


CONTENTS

Page

REVIEW ARTICLE
815 Synthesis and Application of Allyltin Derivatives in Organic Chemistry
— Jarosz S. and Kozlowska E.
INORGANIC CHEMISTRY
832 Synthesis and Magnetism of Binuclear Iron(II) Complexes Bridged by Terephthalato
Dianions

— Li Y.T., Yan C.W. and Liao D.Z.
839 New Antiferromagnetic Dinuclear Complexes of Manganese(II) with 1,8-Naphthalato as Bridging Ligand: Synthesis, Spectrum and Magnetism
— Gao J., Ma S.L. and Liao D.Z.
844 Synthesis and Ferromagnetic Oxamido-Bridged Heterodinuclear Copper(II)-Chromium(III) Complexes
— Yan C.W. and Li Y.T.
852 Synthesis, Spectral and Electrochemical Characterization of Transition Metal Homodi-
nuclear Complexes (Co2+, Cu2+, Ni2+) with Macrocyclic 34-Membered Hexaamine

— Pietraszkiewicz M., Pietraszkiewicz O., Bujno K. and Bilewicz R.
PHYSICAL CHEMISTRY
860 Structural and Surface Properties of Active Carbons Oxidized with Nitric Acid at High
Temperature

— Choma J., Jaroniec M., Burakiewicz-Mortka W., Klinik J. and Olejniczak K.
869 Spectral Studies of Some C60 Complexes with TTF-Derived Donors
— Graja A., Tanatar M.A., Li Y.L. and Zhu D.B.
877 On the Solubility of Chain Alcohols in Supercritical Carbon Dioxide
— Gregorowicz J. and Chylinski K.
886 Transport Studies of Inorganic and Organic Cation Across Liquid Membranes Containing Mannich-Base Calix[4]resorcinarenes
— Pietraszkiewicz O., Kozbial M. and Pietraszkiewicz M.
893 Ab Initio S-T Gap Energies and the Triplet Radical Reactivity of Phenyl-, Pyridyl- and 1-Oxido-pyridylnitrenes
— Pietrzycki W. and Tomasik P.
901 Nonlinear Optical Properties of 1-Alkyl-4(2-benzimidazolylidene)-1,4-dihydropyridines and Their Langmuir Film Formation
— Janik R., Kucharski S. and Predota J.
910 Oxidative Dehydrogenation of Isobutane on Nickel and Chromium Oxide Systems Dispersed on Different Supports
— Moriceau P., Grzybowska B. and Barbaux Y.
916 Kinetics of Oxidation of Phenoxyacetic Acids by Quinolinium Fluorochromate

— Karunakaran K.
925 Measurement and Correlation of the Solubility of Crown Ethers in Selected Organic Solvents
— Domanska U.
CRYSTAL AND MOLECULAR STRUCTURES
940 Reaction of Phenyllithium with N-Pivaloyl-2-piperidone
— Maurin J.K., Czarnocki Z. and Burdach A.
COMMUNICATIONS
949 Individual Extraction Constants of Some Univalent Cations in the Water-Nitrobenzene
System

— Makrlik E. and Bozek F.
953 Effect of Anions on the Base-Catalyzed Hydrolysis of Aluminium Chloride Solutions
— Chamberlain D.C.
956 Interaction of the Components in the Ce-Ge-Sb System
— Stetskiv A.O., Pavlyuk V.V. and Bodak O.I.
959 X-ray Investigation of the Ce-Si-Sn System at 670 K
— Stetskiv A.O., Pavlyuk V.V. and Bodak O.I.
962 Phase Equilibria in the Lu-Si-In System at 870 K
— Tyvanchuk Yu.B., Zaremba V.I. and Kalychak Ya.M.
966 The Ag2SnS3-CdS System
— Parasyuk O.V. and Piskach L.V.
BOOK REVIEW
969 S. Romanowski and L. Wojtczak: "Green Functions in Electrochemistry", Kluwer Academic Publishers Ed., Dordrecht, The Netherlands, 1997
— Dutkiewicz E.


ABSTRACTS


815-831

Synthesis and Application of Allyltin Derivatives
in Organic Chemistry

by S. Jarosz and E. Kozlowska
Institute of Organic Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warszawa, Poland
E-mail: sljar@ichf.edu.pl

(Received December 3rd, 1997; revised manuscript January 12th, 1998)

Methods of the preparation of allyltin derivatives are reviewed. Application of these compounds in stereocontrolled organic synthesis is presented.

832-838

Synthesis and Magnetism of Binuclear Iron(II)
Complexes Bridged by Terephthalato Dianions

by Y. T. Li1, C. W. Yan2 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 September 15th, 1997)

Four new terephthalato-bridged iron(II) binuclear complexes of the formula [Fe2(TPHA)L4](ClO4)2, 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); 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 iron(II) ions, each in an octahedral environment are proposed for these complexes. The [Fe2(TPHA)(Me2bpy)4](ClO4)2 (1) and [Fe2(TPHA)(Me2phen)4](ClO4)2 (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, H = -2J S 1 S2, giving the exchange integrals J = -2.15 cm-1 for (1) and J = -3.28 cm-1 for (2). This result indicates the presence of a weak antiferromagnetic spin-exchange interaction between the metal ions within each molecule.

839-843

New Antiferromagnetic Dinuclear Complexes
of Manganese(II) with 1,8-Naphthalato as Bridging
Ligand: Synthesis, Spectrum and Magnetism

by J. Gao1, S.L. Ma1 and D.Z. Liao2
1Department of Food Engineering, Tianjin University of Commerce, Tianjin, 300400, P. R. of China
2Department of Chemistry, Nankai University, Tianjin, 300071, P.R. of China

(Received February 13th, 1996; revised manuscript October 17th, 1997)

Three manganese(II) binuclear complexes have been synthesized, namely [Mn2(NAPH)(L)4(ClO4)2, L is bpy (2,2'-bipyridyl), phen (1,10-phenanthroline) or NO2-phen (5-nitro-1,10-phenanthroline), NAPH denotes the 1,8-naphthalate dianion. Based on IR, elemental analyses and conductivity measurement, these complexes are proposed to have extended NAPH-bridged structures and consist of two manganese(II) in a distorted octahedron environment. The temperature dependence of magnetic susceptibilities of manganese(II) complexes have been studied, giving the exchange integral J = -0.36 cm-1 (bpy); J = -0.49 cm-1 (phen), respectively. These results indicate a weak antiferromagnetic coupling between the paramagnetic ions in the complexes.

844-851

Synthesis and Ferromagnetic Oxamido-Bridged
Heterodinuclear Copper(II)-Chromium(III) Complexes

by C.-W. Yan1 and Y.-T. Li2
1Department of Biology, Qufu Normal University, Qufu Shandong, 273165, P. R. China
2Department of Chemistry, Qufu Normal University, Qufu Shandong, 273165, P. R. China

(Received October 24th, 1997)

Four new m-oxamido heterodinuclear complexes [Cu(oxap)Cr(L)2](NO3)3, where oxap denotes the N,N'-bis(2-aminopropyl)oxamido dianion and L represents 1,10-phenanthroline (phen); 5-nitro-1,10-phenanthroline (NO2-phen); 5-chloro-1,10-phenan-throline (Cl-phen) and 2,2'-bipyridine (bpy), have been synthesized and characterized by elemental analyses, magnetic moments (at room temperature), molar conductivity measurements, and by optical spectroscopy. It is proposed that these complexes present extended oxamido-bridged structures consisting of a copper(II) and a chromium(III) ions, which have a square planar environment and an octahedral environment, respect-
ively. The [Cu(oxap)Cr(bpy)2](NO3)3 (1) and [Cu(oxap)Cr(phen)2](NO3)3 (2) complexes have been further characterized by variable temperature magnetic susceptibility (4.2~300 K), demonstrating the operation of a ferromagnetic interaction between the adjacent copper(II) and chromium(III) ions through oxamido-bridge in both complexes (1) and (2). Based on the spin Hamiltonian, H = 2J S1 S2 the exchange integrals (J) were evaluated as +32.8 cm-1 for (1) and +30.5 cm-1 for (2).

852-859

Synthesis, Spectral and Electrochemical
Characterization of Transition Metal Homodinuclear Complexes (Co2+, Cu2+, Ni2+) with Macrocyclic
34-Membered Hexaamine

by M. Pietraszkiewicz1, O. Pietraszkiewicz1, K. Bujno2 and R. Bilewicz2
1Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Kasprzaka 44/52, Poland 2Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland

(Received November 6th, 1997; revised manuscript December 24th, 1997)

34-membered macrocyclic hexaamine containing two independent N3 donor sets forms homodinuclear transition metal complexes with cobalt(II), copper(II), and nickel(II). Titration experiments show that the homodinuclear complexes are formed exclusively without formation of mononuclear complexes. Displacements of anions within the copper(II) complexes occur easily upon addition of different anions to the CuCl2 complex. All new complexes are characterized by elemental analysis, IR and UV/VIS spectroscopy, and cyclic voltammetry. The dinuclear Cu(II) complex both in the solution and immobilized in Nafion layer on the electrode undergoes reversible 1e reduction independently at each copper center and exhibits catalytic activity towards oxygen reduction.

860-868

Structural and Surface Properties of Active Carbons Oxidized with Nitric Acid at High Temperature

by J. Choma1, M. Jaroniec2, W. Burakiewicz-Mortka1,
J. Klinik3 and K. Olejniczak4
1Institute of Chemistry, Military Technical Academy, 01-489 Warsaw, Poland
2Separation and Surface Science Center, Department of Chemistry,
Kent State University, 44-242 Kent, Ohio, USA
3Faculty of Fuels and Energy, Academy of Mining and Metallurgy, 30-059 Cracow, Poland
4Institute of Mining, 40-166 Katowice, Poland

(Received November 4th, 1997)

The effect of oxidation of active carbons with nitric acid at the boiling temperature on their structural and surface properties was analyzed by nitrogen and water vapor adsorption data. Adsorption isotherms on unmodified and oxidized active carbons were measured at 77 K for nitrogen and 298 K for water vapor. This oxidation of active carbons led to formation of a significant amount of oxygen acidic groups on their surfaces. Simultaneously this oxidation led to a considerable degradation of the porous structure, which is manifested by decreasing: the total surface area, the micropore volume, and the external surface area of mesopores. However, adsorption of water vapor on oxidized active carbons in low and moderate pressures is considerably greater than on unmodified carbons.

869-876

Spectral Studies of Some C60 Complexes
with TTF-Derived Donors

by A. Graja1, M.A. Tanatar1,2, Y.L. Li3 and D.B. Zhu3
1Institute of Molecular Physics, Polish Academy of Sciences, 60-179 Poznan, Poland
2Institute of Surface Chemistry, Ukrainian Academy of Sciences, Kiev, Ukraine
3Institute of Chemistry, Chinese Academy of Science, Beijing, China

(Received September 18th, 1997; revised manuscript December 18th, 1997)

Electronic and vibrational spectroscopies were applied to the study of the strength of the donor-acceptor interaction and optical properties of the complexes of C60 with two TTF-derived donors, i.e. bis(methylthio)ethylenedithio-tetrathiafulvalene (C1TET-TTF) and tetramethyltetraselenafulvalene (TMTSF). The investigations of the single crystalline samples, for various light polarizations and temperatures, were performed. The analysis of all the spectral data shows that the investigated compounds are weak complexes with a neutral ground state.

877-885

On the Solubility of Chain Alcohols
in Supercritical Carbon Dioxide

by J. Gregorowicz and K. Chylinski
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland E-mail: gregor@ichf.edu.pl

(Received October 6th, 1997; revised manuscript December 19th, 1997)

The phase behaviour in the CO2-n-alkanol family was presented and its influence on the solubility measurements was discussed. A linear relationship is suggested between the logarithm of solubility of liquid n-alkanols in supercritical CO2 and the carbon number of the solute. The hypothesis based on experimental data is supported by thermodynamic considerations. Solubilities of 1-hexanol at 311 K and 1-decanol at 313 K were measured in order to extend the group substances studied in this paper.

886-892

Transport Studies of Inorganic and Organic Cations Across Liquid Membranes Containing Mannich-Base Calix[4]resorcinarenes

by O. Pietraszkiewicz, M. Kozbial and M. Pietraszkiewicz
Institute of Physical Chemistry, Polish Academy of Sciences, 01224 Warsaw, Kasprzaka 44/52, Poland

(Received October 29th, 1997; revised manuscript December 22nd, 1997)

Three calix[4]resorcinarenes, two of them incorporating Mannich-type amino functions (C2 and C3), have been studied in respect to their ionoselectivities towards inorganic alkali cations as well as for organic primary ammonium cations, by ion transport across the bulk liquid membrane and extraction experiments. The ligand C3 displayed particular ionoselectivity for lithium ion, as a carrier in toluene membrane. The discrimination of organic primary ammonium ions was remarkable in liquid membranes, and the pattern of this discrimination depended on the membrane composition. Selectivities for both inorganic and organic ions depended significantly on the membrane composition, the substituent in the calix[4]resorcinarene, and the counterion present in the salts studied.

893-900

Ab Initio S-T Gap Energies and the Triplet Radical
Reactivity of Phenyl-, Pyridyl- and
1-Oxido-pyridylnitrenes

by W. Pietrzycki and P. Tomasik
Department of Chemistry, University of Agriculture, Mickiewicz Av. 21, 31-120 Krakow, Poland
E-mail: rrpietrz@cyf-kr.edu.pl

(Received May 9th, 1997; revised manuscript January 9th, 1998)

The geometric parameters of phenylnitrene, all the isomeric pyridylnitrenes and 1-oxido-pyridylnitrenes in their lowest singlet and triplet states were found employing SCF/6-311G calculations. Singlet EiS and triplet EiT lowest state energies of the corresponding nitrene structures were calculated using both SCF/6-311G as well as MP2/6-311G methods. The EiS energies of nitrenes correspond with their closed shell (RHF) configurations, whereas EiT energies are related to open shell (UHF) configurations. Following the analysis of the gap energies, Eigap = EiT - EiS, electronic -spin orbital density excesses (tN), the total atomic -spin density excesses (TN) on the N nitrene nitrogen atom as well as on the 1-oxide oxygen atom (TO) and the triplet radical reactivity of these nitrenes are explained.

901-909

Nonlinear Optical Properties of 1-Alkyl-4(2-benzimidazolylidene)-1,4-dihydropyridines and Their Langmuir Film Formation

by R. Janik, S. Kucharski and J. Predota
Institute of Organic and Polymer Technology, Wroclaw Technical University,
ul. Wyspianskiego 27, 50-370 Wroclaw, Poland
E-mail: kucharski@itots.ch.pwr.wroc.pl

(Received November 24th, 1997; revised manuscript January 9th, 1998)

The nonlinear optical properties of a homologous series of heterocyclic betaines (1-alkyl-4(2-benzimidazolylidene)-1,4-dihydropyridines) with methyl, n-butyl, n-octyl, n-dodecyl and n-hexadecyl alkyl groups were evaluated by determination of their first hyperpolarizability (ß) using solvatochromic method. The measurements showed that static (ß0) and in external field (ß1064) first hyperpolarizability values for the betaines were 2.5-3.5 and 4-5 times higher than that for p-nitroaniline, respectively. The Langmuir monolayer formation of the compounds on aqueous surface was evaluated by the surface pressure () vs. molecular area per molecule () isotherms. The betaines with n-dodecyl and n-hexadecyl chains were able to form a Langmuir film, although the shape of - isotherms indicated that they would not be qualified as good film forming materials of single component films.

910-915

Oxidative Dehydrogenation of Isobutane on Nickel
and Chromium Oxide Systems Dispersed
on Different Supports

by P. Moriceau1, B. Grzybowska2 and Y. Barbaux3
1Laboratoire de Catalyse Homogene et Heterogene, URA CNRS 402,
Universite des Sciences et Technologies de Lille, 59655 Villeneuve d'Ascq Cedex, France 2Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences,
30-239 Krakow, ul. Niezapominajek 3, Poland 3Universite d'Artois, Faculte des Sciences Jean Perrin, BP 18, 62307 Lens Cedex, France

(Received December 2nd, 1997; revised manuscript January 12th, 1998)

Nickel oxide and chromia supported on ThO2, CeO2, MgO and SiO2 have been tested in oxidative dehydrogenation of isobutane. Both NiO- and Cr2O3-based systems have been found active in this reaction already around 300oC, the catalytic performance being dependent on the nature of the support. Chromia-based catalysts are more active and selective as compared with the NiO-based ones. The highest activity and selectivity have been observed for the CrOx/CeO2 system. The basicity of the catalysts determined by a probe reaction of the isopropanol dehydrogenation follows the same sequence as the total activity in the oxidative dehydrogenation of isobutane, which suggests an activat-ion of the C-H bond on basic centres of the catalysts.

916-924

Kinetics of Oxidation of Phenoxyacetic Acids
by Quinolinium Fluorochromate

by K. Karunakaran
Department of Chemistry, Adhiyamaan College of Engineering , Hosur - 635 109, India

(Received July 28th, 1997; revised manuscript January 21st, 1998)

The kinetics of oxidation of twenty one phenoxyacetic acids by quinolinium fluoro- chromate have been studied in binary solvent mixtures. Acrylonitrile has no effect on the rates of oxidation in dipolar protic solvent but in a aprotic solvent it decreases the oxidation rates. In both solvent systems there exists an equilibrium prior to the rate limiting step, followed by irreversible decomposition of the complex. The calculated rate constants correlate well with Hammett values. Suitable mechanisms have been proposed.

925-939

Measurement and Correlation of the Solubility
of Crown Ethers in Selected Organic Solvents

by U. Domanska
Warsaw University of Technology, Faculty of Chemistry, 00-664 Warsaw, Poland
E-mail:ula@ch.pw.edu.pl

(Received December 2nd, 1997; revised manuscript January 26th, 1998)

The solid-liquid equilibrium (SLE), of 13 binary mixtures {18-crown-6 (1) + selected organics solvents: benzene, 1-heptene, 1-heptyne, tert-butanol, ethyl methyl ketone, methyl n-propyl ketone, isobutyl methyl ketone, 1-hexanal, epichlorohydrin, DMSO, 1,1,1-trichloroethane, tetrachloroethylene, 1-chlorobutane (2)} have been determined between 240-315 K. The data have been correlated with three GE equations: Wilson, NRTL and UNIQUAC. Moreover published earlier nineteen sets of SLE data for different crown ether: {12-crown-4 or 18-crown-6, or dibenzo-8-crown-6, or dibenzo-24-crown-8 (1) + organic solvent (2)} published earlier have been examined, using the same correlation equations. The best correlation of the solubility data have been obtained by Wilson's equation, where the root-mean-square deviations of the solubility temperatures varied from 0.44 K to 1.87 K and were dependent on the solute calculated. In the calculations, the existence of solid-solid first-order phase transition in 18-crown-6 and dibenzo-24-crown-8 have been taken into consideration.

940-948

Reaction of Phenyllithium
with N-Pivaloyl-2-piperidone

by J.K. Maurin1,2, Z. Czarnocki3 and A. Burdach3
1Institute of Atomic Energy, 05-400 Otwock-Swierk, Poland
2Drug Institute, Chelmska 30/34, 00-725 Warsaw, Poland
3Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland

(Received October 23rd, 1997; revised manuscript January 16th, 1998)

Structural features of the reaction of N-pivaloyl-2-piperidone with phenyllithium were elaborated. Two compounds (4) and (5) were obtained and their structures were established by X-ray analysis. C16H23NO2 (4): monoclinic, C2/c, a = 37.197(7), b = 8.479(2), c = 9.988(2) Å, ß = 96.51(3)o, Z = 8; C22H27NO (5): orthorhombic, P212121, a = 8.244(2), b = 10.305(2), c = 22.616(5) Å, Z = 4.

949-952

Individual Extraction Constants of Some Univalent
Cations in the Water-Nitrobenzene System

by E. Makrlik1 and F. Bozek2
1Department of Chemistry, Charles University, Faculty of Education,
M.D. Rettigove 4, 116 39 Prague 1, Czech Republic
2Military Academy of Ground Forces, 683 03 Vyskov, Czech Republic

(Received October 27th, 1997

953-955

Effect of Anions on the Base-Catalyzed Hydrolysis
of Aluminium Chloride Solutions

by D.C. Chamberlain
FMH, 74 Ragstone Road, Slough, Berks, SL1 2PX, England, E-mail 106054.3434@compuserve.com

(Received November 11th, 1997; revised manuscript December 29th, 1997)

956-958

Interaction of the Components in the Ce-Ge-Sb System

by A.O. Stetskiv, 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 December 1st, 1997; revised manuscript January 26th, 1998)

959-961

X-ray Investigation of the Ce-Si-Sn System at 670 K

by A.O. Stetskiv, 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 November 12th, 1997; revised manuscript January 26th, 1998)

962-965

Phase Equilibria in the Lu-Si-In System at 870 K

by Yu.B. Tyvanchuk, V.I. Zaremba and Ya.M. Kalychak
Inorganic Chemistry Department, Ivan Franko Lviv State University,
Kyryla and Mefodiya Street. 6, 290005 Lviv, Ukraine

(Received December 22nd, 1997; revised manuscript January 30th, 1998)

966-968

The Ag2SnS3-CdS System

by O.V. Parasyuk and L.V. Piskach
Department of Inorganic and Physical Chemistry,
Volyn State University, Voli av.13, Lutsk 263009, Ukraine

(Received December 1st, 1997; revised manuscript January 30th, 1998)

969-970

S. Romanowski and L. Wojtczak: "GREEN FUNCTIONS IN ELECTROCHEMISTRY",
Kluwer Academic Publishers Ed., Dordrecht, The Netherlands, 1997

reviewed by E. Dutkiewicz


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