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Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

 

VOLUME 43A

NUMBER 10

OCTOBER 2004

CONTENTS

 

Papers

 2043

 Ab initio calculation on the effect of  substituents in the alkylation mechanism by nitrogen mustards at N-7 of guanine

 

 

 

 

P K Bhattacharyya & C Medhi*

 

 Ab initio calculation of some DNA binding drugs, nitrogen mustards, has been reported for studying the effect of substituents in the alkylation reaction. The substituents do not affect the formation of aziridinium ion of most drugs but for bendamustine and some model drugs of nitrogen mustards with ethyl and ethoxy group substituents,, the energies of forming the aziridinium ion are high.

 2049

On the dehydrogenation of 1- and 2-propanols on Cu (111) surface: A UBI-QEP based approach

  

 

 

 

 

F Gobal* & A Eftekhari

 

The method of unity bond index-quadratic exponential has been employed to investigate the energetics of routes to adsorption and decomposition of 1- and 2-propanols on Cu(111) plane. A mechanism based on the formation of surface alkoxide groups and elimination of β-hydrogen to yield exclusively the corresponding aldehyde∕ketone is confirmed on the basis of the energy criteria.

 2055

Aromatization of methane under non-oxidative conditions over molybdenum containing molecular sieves with MFI & MEL topologies

 

 

 

 

 

P S Raghavan

 

 Molybdenum containing molecular sieves with MFI and MEL topologies have been synthesized hydrothermally and characterized using XRD and BET surface area. The activity of these catalysts for the conversion of methane to benzene has been examined at 958 K, under non-oxidative conditions. The hydrothermally synthesized Al and Mo containing molecular sieves are found to be efficient for the above reaction.

 2060

Esterification of isoamyl alcohol using solid acid catalysts

 

 

 

 

 

 

N Nagaraju* & S Z Mohamed Shamshuddin

 

 Catalytic activity of different solid acids obtained by calcination of hydroxides of Al, Si, Zr and Ti as well as their sulfated forms has been reported in liquid phase esterification of isoamyl alcohol with propionic acid. The major product of the catalytic reaction has been found to be isoamyl propionate. The yield (%) of the ester has been found to depend on the textural properties, total surface acidity and surface area of the catalysts. 

2066

Methacrylonitrile-vinylidene chloride-butyl acrylate terpolymers: Monomer sequence determination by one- and two-dimensional NMR spectroscopy

 

 

 

 

A S Brar*, D R Pradhan & Sunita Hooda

 

Methacrylonitrile-vinylidene chloride-butyl acrylate terpolymers of different compositions have been prepared by bulk polymerisation and their compositions determined from quantitative assessment of the respective 13C{1H} NMR spectra. The complete 1H and 13C{1H} NMR spectra of terpolymers have been assigned without ambiguity with the help of 2D HSQC NMR spectroscopic techniques.

2073

Studies of osmotic coefficients and volumetric behaviour on aqueous solutions of b-cyclodextrin at 298.15 K

 

 

 

 

 

Dilip H Dagade, Rahul R Kolhapurkar & Kesharsingh J Patil*

 

The osmotic coefficient, solute activity coefficients and apparent molar volume are determined for b-cyclodextrin using the techniques of vapor pressure osmometry and digital densitometer in aqueous solutions at 298.15 K. Using the partial molar volume data at infinite dilution and B*2 value, the contribution due to solute-solvent and solute-solute interactions in terms of attractive and repulsive components are estimated. The results are discussed in terms of hydrophobic hydration and hydrophobic interaction.

2081

Coenzyme B12 model studies: Equilibria and kinetics of axial ligation of trifluoroethyl(aquo)- cobaloximes by N donor ligands

 

 

 

 

D Sudarshan Reddy, M Bhoopal, N Navaneetha & S Satyanarayana*

 

   kon

RCo(DH)2H2O + L                           RCo(DH)2.+ H2O

                                           koff         

                                               

                   -H+              + H+

 

                           LH+

2087

Kinetics and mechanism of substitution of aqua ligands from cis-diaqua-bis-(bipyridyl) ruthe-nium(II) complex by glutathione in aqueous medium

 

 

A Goswami & K De*

 

The kinetics of substitution of aqua ligands from cis-diaqua-bis-(bipyridyl) ruthenium(II) complex by glutathione (reduced; GSH) have been studied spectrophotometrically as a function of [glutathione], [Ru(bipy)2(H2O)22+] and temperature at pH 4.8. From the data a reaction mechanism involving SN2 path has been suggested.

Notes

2091

 

Solid solutions of strontium-calcium hydroxy-lapatites containing arsenate

 

 

 

 

 

P N Patel* & S Panda

 

Homogeneous solid solutions of strontium-calcium hydroxylapatite containing arsenate, Ca10-nSrn(PO4)6-m(AsO4)m-(OH)2, with fixed n = 1, have been prepared over the entire compositional range by co-precipitation in aqueous media. The infrared spectra and lattice constants of the solid solutions have been found to vary linearly with composition between those of the pure end members.

2094

Synthesis and characterization of terpolymer of a-terpineol, styrene and methylmethacrylate: A kinetic study

 

 

 

 

 

 

 

 

 

 

Sarika Yadav & A K Srivastava*

 

 

2098

Effect of ultrasound on the redox reactions of iron (II) and (III)

 

 

 

 

 

Pankaj* & Manju Chauhan

 

The phenomenon of cavitation, generated through ultrasound, is found to facilitate both oxidation and reduction reactions of iron. Under ultrasonic field a solution of Fe(II) oxidizes to Fe(III) and forms a pink coloured complex of [Fe(SCN)6]3-, whereas Fe(III) reduces to Fe(II) and complexes with K3 [Fe(CN)6] to form a prussian blue solution. A possible mechanism for inter-conversion has also been discussed.

2102

Ultrasonic behaviour and study of molecular interactions of substituted azole in N,N-dimethylformamide at different temperatures and concentrations

 

 

 

 

 

Deepali P Gulwade*, M L Narwade & K N Wadodkar

 

Ultrasonic velocity and density measurements of 2-(4-amino-5-mercapto- [1,2,4] triazol-3-yl)- phenol in N,N-dimethylformamide have been carried out at 303, 308, 313 and 318 K in the concentration range 2 10 10-3 mol dm-3. Different acoustic properties like apparent molal volume, apparent molal compressibility, intermolecular free length, specific acoustic impedance and relative association have been determined. These parameters have been interpreted in terms of solute-solvent and solute-solute interactions.

2105

Kinetics and mechanism of acid assisted reduction of unsymmetrical chelate complex [CoIII(Am) (endibigH) (ClO4)2] (where Am = amino acid and endibigH = ethylenedibiguanide)

 

 

 

Asim Kumar Majee, D D Chaturvedi, Abhishek Srivastava, Abhinav Agarwal, R M Naik* & P C Nigar

 

 

                                            [Co(Am)(endibigH2)]3+

 

 

                                       + Oxidised product of endibigH

 2109

Mechanism of oxidation of  p-nitroaniline by  ammonium metavanadate in sulphuric acid medium : A kinetic approach

 

 

 

 

 

 

 

Madhavi Verma* & Chetna Tekchandani

 

 The kinetics of ammonium metavanadate oxidation of  p-nitroaniline in sulphuric acid medium has been followed spectrophotometrically. The reaction follows second order kinetics being unity in each of the reactants. The stoichiometry of the reaction has been found to be 1:1. The effect of various parameters viz., [oxidant], [substrate], [H+], ionic strength, dielectric constant and added micelles have been investigated and the thermodynamic parameters have been evaluated. A suitable mechanism consistent with the experimental results has also been proposed.

2113

 

Silyl nitrogen compound: Part XV Reactions of nonmetal halides with silylated tosylhydrazines

 

 

 

 

 

 

S K Vasisht* & Anuradha Sharma

 

 

2120

Synthesis, characterization, biological and thermal properties of some new Schiff base complexes derived from 2-hydroxy-5-chloro-acetophenone and S-methyldithiocarbazate

 

 

 

 

 

 

 

  

 

 

 

 

 

J T Makode & A S Aswar*

 

 

 

M=Mo(II), Co(II) and Ni(II)

 

  

 

M = Cu(II), Zn(II) & Cd(II)

 2126

 Cation-p interactions. Synthesis and crystal structure of complexes [K(B18-C-6)]NCS and [K(DB18-C-6)]2[Hg(SCN)4]

 

 

 

 

 

 

 

 

 

 

Yuehua Zhu, Jianmin Dou*, Dacheng Li & Daqi Wang

 

 

 2132

 

Synthesis, characterisation and biological activities of ruthenium(II) Schiff base complexes

 

 

 

 

 

 

 

 

 

M Periyasamy, K P Balasubramanian & V Chinnusamy* 

 

 

 Authors for correspondence are indicated by (*)

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2043-2048

 

Ab initio calculation on the effect of substituents in the alkylation mechanism by nitrogen mustards at N-7 of guanine

P K Bhattacharyya & C Medhi*

 

Ab initio calculations of some DNA binding drugs, nitrogen mustards, have been performed for studying the effect of substituents in the alkylation reaction. The aziridinium ion of different drugs having different substituents has been studied. The substituents do not affect the formation of aziridinium ion of most drugs but for bendamustine and some model drugs of nitrogen mustards with substituents, ethyl and ethoxy groups, the energies of forming the aziridinium ion are high. The geometrical parameters of the aziridinium ions of drugs remain almost the same. However in bendamustine and some other derivatives of nitrogen mustards, distortion of aziridinium rings are observed. The results do not basically encourage the modification drugs with various substituents in the process of designing new drugs of enhanced alkylating ability. Unlike other drugs, bendamustine and some derivatives may generate carbonium ion in the intermediate state of alkylation.

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2049-2054

 

On the dehydrogenation of 1- and 2-propanols on
Cu(111) surface: A UBI-QEP based approach

F Gobal* & A Eftekhari

 

The method of unity bond index-quadratic exponential potential (UBI-QEP) has been employed to investigate the energetics of routes to adsorption and decomposition of 1- and 2-propanols on Cu(111) plane. Both the clean and pre-adsorbed oxygen containing surfaces have been considered. A mechanism based on the formation of surface alkoxide groups which become more favored in the presence of adsorbed oxygen and further elimination of β-hydrogen to yield exclusively the corresponding aldehyde∕ketone is confirmed on the basis of the energy criteria. The latter process is somewhat hindered in the presence of surface oxygen. The early adsorption of water and the lack of H/D scrambling as reported previously have been rationalized.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2055-2059

 

Aromatization of methane under non-oxidative conditions over molybdenum containing molecular sieves with MFI and MEL topologies

P S Raghavan

 

Molybdenum containing molecular sieves with MFI and MEL topologies have been synthesized hydrothermally and characterized using XRD and BET surface area. The activity of these catalysts for the conversion of methane to aromatics (benzene) has been examined at 958 K, under non-oxidative conditions. The results are compared with those obtained over H-ZSM-5 and Mo impregnated H-ZSM-5 catalysts. The hydrothermally synthesized Al and Mo containing molecular sieves are found to be efficient for the above reaction. An optimum amount of Mo is required to drive and sustain the reaction.

 

IPC Code: Int. Cl.7  B01J  29/076

 

 

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2060-2065

 

Esterification of isoamyl alcohol using solid acid catalysts

N Nagaraju* & S Z Mohamed Shamshuddin

 

Catalytic activity of different solid acids obtained by calcination of hydroxides of Al, Si, Zr and Ti as well as their sulfated forms has been investigated in liquid phase esterification of isoamyl alcohol with propionic acid. The catalysts have been characterized for their textural properties, surface acidity, surface area and sulfur content. The major product of the catalytic reaction has been found to be isoamyl propionate. The yield (%) of the ester has been found to depend on the textural properties, total surface acidity and surface area of the catalysts. In the case of sulfated zirconia which exhibited highest acidity, isoamyl ether has also been formed to an extent of 0.6-4.5%. Effects of amount of catalyst, duration of the reaction and the molar ratios of the reactants on the yield of ester have been studied. A plausible reaction mechanism for the formation of isoamyl propionate is described.

 

IPC Code: Int. Cl.7 C07C 67/00; B01J 21/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2066-2072

 

Methacrylonitrile-vinylidene chloride-butyl acrylate terpolymers: Monomer sequence determination by one- and two-dimensional NMR spectroscopy

A S Brar*, D R  Pradhan  & Sunita Hooda

 

Methacrylonitrile-vinylidene chloride-butyl acrylate (M/V/B) terpolymers of different composition have been prepared by bulk polymerization using benzoyl peroxide as an initiator. The terpolymer compositions have been determined from quantitative assessment of the respective  13C{1H} NMR spectra and the observed values compared with the theoretical values obtained from Alfrey-Goldfinger's equation. The overlapping methine and methylene carbon resonances of terpolymers have been differentiated by DEPT experiments. The quaternary carbon resonances of M/V/B terpolymers have been assigned to triad compositional sequences. The complete 1H and 13C{1H} NMR spectra of terpolymers have been assigned without ambiguity with the help of 2D HSQC NMR spectroscopic techniques.

 

IPC Code: Int. Cl.7 C08F 120/42; G01R 33/20

 

 

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2073-2080

 

Studies of osmotic coefficients and volumetric behaviour on
aqueous solutions of b-cyclodextrin at 298.15 K

Dilip H Dagade, Rahul R Kolhapurkar & Kesharsingh J Patil*

 

The osmotic coefficient, solute activity coefficients and apparent molar volume are determined for b-cyclodextrin  (b-CD) using the techniques of vapor pressure osmometry and digital densitometer in aqueous solutions (0.00164 to 0.01308 mol kg-1) at 298.15 K. The thermodynamic data of activities and partial molar volumes for solvent and solute are computed using appropriate methodology and equations. Theories of dilute solutions such as McMillan-Mayer and Flory-Huggins are applied to estimate the second virial coefficient (B*2) for b-CD, the number of binding sites and c12 interaction parameter. Using the partial molar volume data at infinite dilution and B*2 value, the contribution due to solute-solvent and solute-solute interactions in terms of attractive and repulsive components are estimated. The values of B*2 and the components are compared with the values reported for mono-saccharides, disaccharides and other non-electrolytes. The results are discussed in terms of hydrophobic hydration and hydrophobic interaction.

 

IPC Code : Int. Cl.7 G01N 13/04

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2081-2086

 

Coenzyme B12 model studies: Equilibria and kinetics of axial ligation of trifluoroethyl(aquo)cobaloximes by N donor ligands

D Sudarshan Reddy, M Bhoopal, N Navaneetha & S Satyanarayana *

 

Equilibria and kinetics of the reaction of trifluroethyl(aquo)cobaloxime with imidazole and substituted imidazoles have been studied as a function of pH at 25C, 1.0 M ionic strength(KCl) by UV-vis spectrophotometry. Comparison of equillibrium constants with respect to ligand are in the order K1-Meimd> K Imd> K2-Meimd > K1, 2-Dimeimd > K2-Etimd which are correlated to basicity and steric factors. The equilibrium constants are correlated to the softness and ability to form dp-pp back bonding.

 

IPC Code: Int Cl.7 C07C 251/70; C07D 233/54

 

 

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2087-2090

 
Kinetics and mechanism of substitution of aqua ligands from cis-diaqua-bis-(bipyridyl) ruthenium(II) complex by glutathione in aqueous medium

A Goswami & K De*

 

 

The kinetics of substitution of aqua ligands from cis-diaqua-bis-(bipyridyl) ruthenium(II) complex by glutathione (reduced; GSH) have been studied spectrophotometrically as a function of [Ru(bipy)2(H2O)22+], [glutathione] and temperature at pH 4.8.  The following rate law has been established, d[Ru(bipy)2 (H2O)22+]/dt = k2[Ru(bipy)2 (H2O)22+] [glutathione]

where k2 is the second order rate constant.  The rate increases with increase in pH in the range 4.0-5.6.  The anation rate and activation parameters of this system have been calculated and compared with those of a few other anation reactions of the same complex.  From all these data a reaction mechanism involving SN2 path has been suggested. A plausible mechanism indicating the nature of the activated complex has been proposed.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, October 2004, pp. 2091-2093

 

Solid solutions of strontium-calcium hydroxylapatites containing arsenate

P N Patel* & S Panda

Homogeneous solid solutions of strontium-calcium hydroxylapatite containing arsenate, Ca10-nSrn(PO4)6-m(AsO4)m-(OH)2, with fixed n = 1, have been prepared over the entire compositional range by co-precipitation in aqueous media. The infrared spectra and lattice constants of the solid solutions have been measured and found to vary linearly with composition between those of the pure end members.

 

IPC Code: C01F 11/02

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2094-2097

 

Synthesis and characterization of terpolymer of a-terpineol, styrene and methylmethacrylate: A kinetic study

Sarika Yadav & A K Srivastava*

 

Synthesis of a series of functional terpolymers, consisting of two electron donating monomers viz. a-terpineol and styrene with one electron accepting monomer i.e. methylmethacrylate, using benzoylperoxide as radical initiator and xylene as diluent at 80C for 2 h has been studied. The system follows ideal kinetics with an overall activation energy 23 kJ/mol. The formation of the terpolymer is confirmed by 1H NMR and FTIR spectrum. The reactivity ratios calculated using Kelen-Tdos method are r1 (MMA) = 0.85 and r2 (styrene + a-terpineol) = 0.17.

 

IPC Code: Int.Cl.7 C08F 2/04

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2098-2101

 

Effect of ultrasound on the redox reactions of iron (II) and (III)

Pankaj* & Manju Chauhan

 

The standard electrode potential of Fe3+/Fe2+ (+0.77V) is very close to the mid-point value of 0.8V in the electrode potential series. The oxidation and reduction of iron from oxidation state II to III and vice versa is therefore possible theoretically with equal ease. This has been examined experimentally and the phenomenon of cavitation, generated through ultrasound, is found to facilitate both oxidation and reduction reactions of iron. Under ultrasonic field a solution of Fe(II) oxidizes to Fe(III) and forms a pink coloured complex of [Fe(SCN)6]3-, whereas Fe(III) reduces to Fe(II) and complexes with K3[Fe(CN)6] to form a prussian blue solution. A possible mechanism for inter-conversion has also been discussed.

 

IPC Code: B01J 19/10

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2102-2104

 

Ultrasonic behaviour and study of molecular interactions of substituted azole in
N,N-dimethylformamide at different temperatures and concentrations

Deepali P Gulwade*, M L Narwade & K N Wadodkar

 

Ultrasonic velocity and density measurements of 2-(4-amino-5-mercapto-[1,2,4] triazol-3-yl)-phenol [AMTP] in N,N-dimethylformamide (DMF) have been carried out at 303, 308, 313 and 318 K in the concentration range 2-1010-3 mol dm-3. Different acoustic properties like apparent molal volume, apparent molal compressibility, intermolecular free length, specific acoustic impedance and relative association have been determined. The results of the present study suggest the presence of molecular interactions in DMF. These parameters have been interpreted in terms of solute-solvent and solute-solute interactions.

 

IPC Code: Int. Cl.7 B01J 19/10

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2105-2108

 

Kinetics and mechanism of acid assisted reduction of unsymmetrical chelate complex [CoIII(Am) (endibigH) (ClO4)2] (where Am = amino acid and endibigH = ethylenedibiguanide)

Asim Kumar Majee, D D Chaturvedi, Abhishek Srivastava, Abhinav Agarwal, R M Naik*&  P C Nigam

 

The acid mediated dissociation of three mixed chelate complexes of cobalt(III) containing a common primary quadridentate ligand ethylenedibiguanide and secondary bidentate amino acid anions, viz., glycinate, a-alaninate and valinate have been investigated spectrophotometrically at 490 nm to study the influence of chelate size, ring pattern, bonding nature and basicity of the ligand on the dissociation rates. The kobs values for all these complexes vary linearly with [HCIO4] having a positive slope and no intercept. The reactivity order of the complexes is: DL-valinato < a-alaninato < glycinato. For all these complexes, solvent assisted metal-ligand bond rupture is proposed. The reactions have been studied as a function of ionic strength, dielectric constant of the medium and temperature. The activation parameters have been evaluated and used in support of the proposed mechanistic scheme.

 

IPC Code: Int Cl.7 C07B 35/02

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2109-2112

 

Mechanism of oxidation of p-nitroaniline by ammonium metavanadate
in sulphuric acid medium: A kinetic approach

Madhavi Verma* & Chetna Tekchandani

 

The kinetics of  ammonium metavanadate oxidation of p-nitroaniline in sulphuric acid medium has been followed spectrophotometrically. The reaction follows second order kinetics being unity in each of the reactants. The stoichiometry of the reaction has been found to be 1:1. The effect of various parameters viz.[oxidant], [substrate], [H+], ionic strength, dielectric constant and added micelles have been investigated and the thermodynamic parameters have been evaluated. p-Benzoquinone has been identified as the main oxidation product by chromatographic and UV spectrophotometric techniques. A suitable mechanism consistent with the experimental results has also been proposed.

 

IPC Code: Int Cl7. C07B 33/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2113-2119

 

Silyl nitrogen compound: Part XV Reactions of nonmetal halides
with silylated tosylhydrazines

S K Vasisht* & Anuradha Sharma

 

Nonmetal halides EXn (E = C, Si, P, As, S; X = Br, Cl) and halogens (X = Br2, I2) react with bis(trimethylsilyl)tosylhydrazine, (Me3Si)2TsN2H to form tosylhydrazides, EXn1(Me3Si)TsN2H, which on heating in vacuum, form a variety of azanes, hydrozones, diazenes and phophazanes. Ditosyltetrazene intermediate formed by dimerisation decomposes into ditosylhydrazine with liberation of nitrogen gas.

 

IPC Code: Int.Cl.7 C0F 7/10

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp.2120-2125

 

Synthesis, characterization, biological and thermal properties of
some new Schiff base complexes derived from 2-hydroxy-5-chloroacetophenone
and S-methyldithiocarbazate

J T Makode & A S Aswar*

 

A new Schiff base derived from 2-hydroxy-5-chloroacetophenone and S-methyldithiocarbazate and its coordination complexes with manganese(II), iron(II) cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and oxovanadium(IV) have been synthesized. The resulting complexes have been characterized on the basis of their elemental analyses, molecular weight, infrared spectra, reflectance spectra, magnetic susceptibilities, molar conductance measurements and thermogravimetric analysis. The Schiff base acts as a tridentate diabasic donor and coordinating through the deprotonated phenolic oxygen, thioenolic sulphur and azomethine nitrogen atoms. The antibacterial activities of the ligand and its complexes have been screened against E. coli, S. aureus, Pr. mirabilis and S. typhi. Various kinetic and thermodynamic parameters have been evaluated from the thermogravimetric data and comparable values are obtained. Solid state conductivity of ligand and its complexes have also been measured from room temperature to about 473 K, in their pellet forms and the chelates are found to show semiconducting behaviour.

 

IPCode: Int. Cl.7. C07F 1/08; C07F 3/06; C07F 3/08; C07F 15/02; C07F 15/04; C07F 15/06

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2126-2131

 

Cation-p interactions. Synthesis and crystal structure of complexes
[K(B18-C-6)]NCS and [K(DB18-C-6)]2[Hg(SCN)4]

Yuehua Zhu, Jianmin Dou*, Dacheng Li & Daqi Wang

 

The reactions of benzo-18-crown-6 (B18-C-6) with K2[Cd(SCN)4] and dibenzo-18-crown-6 (DB18-C-6) with K2[Hg(SCN)4] are reported here. The unexpected complex [K(B18-C-6)]NCS (1) and complex [K(DB18-C-6)]2[Hg(SCN)4] (2) have been isolated and characterized by elemental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P21/c and C2/c respectively with cell dimensions, 1: a = 9.960(3), b = 25.097(7), c = 8.374(2) , b = 106.519(3), V = 2006.7(10) 3, Z = 4, Dcalcd. = 1.356 g/cm3, F(000) = 864, R1 = 0.0429, wR2 = 0.0579 and 2: a = 30.187(17), b = 14.668(8), c = 25.467(15) , b = 99.517(10), V = 11119(11) 3, Z = 8, Dcalcd. = 1.414 g/cm3, F(000) = 4752, R1 = 0.0415, wR2 = 0.0805. Complex 1 forms one-dimensional infinite chain structure through K+-p interactions between neighboring molecules in the solid state. In complex 2, [K(DB18-C-6)]2[Hg(SCN)4] molecules form a dimeric structure bridged by K+-p interactions between adjacent [K(DB18-C-6)] units.

 

IPC Code: Int. Cl.7 C07F 1/06; C07 3/10

 

 

 

Indian Journal of Chemistry

Vol. 43A, October 2004, pp. 2132-2136

 

Synthesis, characterization and biological activities of
ruthenium(II) schiff base complexes

M Periyasamy, K P Balasubramanian & V Chinnusamy*

 

The synthesis and characterization of several hexa-coordinated Ru(II) Schiff base complexes of the type [RuX(CO)(EPh3)BLL1] (E = P or As; X = H or Cl; B = py, pip, PPh3, AsPh3; LL1 = anion of the Schiff bases derived by the condensation of benzhydrazide and furfuraldehyde or 2-furyl methylketone or 2-acetylthiophene) are reported. IR, EPR, electronic spectra and cyclic voltammetric data of the complexes are discussed. An octahedral geometry has been tentatively proposed for all these complexes. The new complexes have been subjected to antibacterial investigations also.

 

IPC Code: Int.Cl.7 C07F 15/00; C07C 251/02