Indian Journal of Chemistry

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

 

VOLUME 46A

NUMBER 8

August 2007

 

CONTENTS

 

 

1221

 

Synthesis, characterization and antimicrobial studies of Sb(III) complexes of substituted thioimines

 

 

 

 

 

 

 

 

 

 

 

 

Karuna Mahajan, Nighat Fahmi & Ran Vir Singh*

 

 

 

 

Antimony complexes of a new class of substituted thioimines have been prepared by reacting Ph3Sb (III) with
[1-(2-naphthyl) ethyledene] hydrazinecarbodithioic acid phenyl methyl ester, [1-(2-thienyl) ethyledene] hydrazinecarbodithioic acid phenyl methyl ester, [1-(2-pyridine) ethyledene] hydrazinecarbodithioic acid phenyl methyl ester and
[1-(2-furanyl)ethyledene] hydrazinecarbodithioic acid phenyl methyl ester, in unimolar and bimolar ratios using thermal as well as microwave method.

 

 

1226

 

Magnetic and spectral properties of adducts of copper(II) chlorobenzoates with substituted piperazines

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

B S Manhas, S B Kalia*, A K Sardana & K Lumba

 

 

 

 

Adducts of Cu(OOCR)2 (where R = 2-, 3- or 4-ClC6H4) with saturated substituted piperazines of the type Cu(OOCR)2(L-L)n [where n = 0.5 or 1 and L-L = 1-methylpiperazine,
1,4-dimethylpiperazine, 2,6-dimethylpiperazine and
1-phenylpiperazine] have been prepared and characterized.

 

 

 

1233

 

Magnetic and spectral studies on cobalt(II) chelates of a dithiocarbazate derived from isoniazid

 

 

 

S B Kalia*, K Lumba, G Kaushal & M Sharma

 

 

 

 

New cobalt(II) dithiocarbazates with different mononegative and dinegative counter anions, of the general formulae
[Co(IN-DtczH)2]Xn (IN-DtczH = isonicotinoyldithiocarbazic acid; X = Cl, Br, NO3, ClO, CH3COO for n = 2 and X = SO4 and C2O4 for n = 1) for Zwitterionic complexes and [Co(IN-Dtcz)2] for a normal complex have been prepared.

 

 

1240

 

Homogeneous catalysis of aquachlororuthenium(III) complex and evaluation of individual kinetic and thermodynamic parameters of bromate-lactic acid redox reaction at low and high acid strengths

 

 

 

 

 

 

 

 

 

 

Ch Sanjeeva Reddy* & T Vijaya Kumar

 

 

 

 

The mechanism of aquachlororuthenium(III) complex catalysed oxidation of lactic acid is [acid] independent. At low acid strength, the proposed mechanism involves oxidation of the Ru(III)-substrate complex by bromic acid through complexation to Ru(V)-substrate intermediate in the rate-determining step. The complex subsequently decomposes into CH3CHO and CO2 through C-C bond cleavage with regeneration of Ru(III) in the fast step. At high acid strength, the mechanism involves oxidation of Ru(III) to Ru(V) by Br(V) followed by the ternary complex formation between the formed Ru(V) and the preformed Ru(III)-substrate binary complex, which decomposes into products in the rate-determining step with regeneration of the catalyst.

 

 

1252

 

Electrochemistry of [Fe4S4(SCH2CH2COO-)4]6- in liposomes and microemulsions

 

 

 

 

 

 

 

 

 

 

 

 

 

Raben Ch Roy, Diganta Kumar Das* & Biva Das

 

 

 

 

[Fe4S4(SCH2CH2COO-)4]6-, a structural analogue of the active center of ferredoxin and P cluster of nitrogenase, shows two distinct reversible couples with redox potential of –643±5 mV and
–972±5 mV versus Ag-AgCl respectively due to 3+/2+ and 2+/1+ couples of the core [Fe4S4] in liposomes.

 

 

Notes

 

1257

 

Ionic effects on some anticancer drugs from analysis of their metal ion and proton affinities

 

 

 

 

 

 

 

 

P K Bhattacharyya, Murshida Karim & C Medhi*

 

 

 

 

The proton affinities and the metal ion affinities of nitrogen mustards have been investigated to analyze the ionic effect in alkylation reactions.

 

 

 

1263

 

Determination of acid dissociation constants of some monobasic organic acids in acetonitrile from molar conductance

 

 

 

 

 

 

 

 

Samik Nag & Dipankar Datta*

 

 

 

 

The pKa values of 14 monobasic organic acids like carboxylates, phenols, etc., are determined in acetonitrile from conductivity measurements. These pKa values are found to be higher than those reported in the aqueous medium on the average by 2.8 (± 1.1) pKa units.

 

1266

 

Preparation of silver nanoparticles by heating a quaternary ammonium polyelectrolyte-AgNO3 aqueous solution in basic conditions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yonglan Luo

 

 

 

 

Silver nanoparticles (2 nm in size)have been prepared by heating an aqueous solution containing quaternary ammonium polyelectrolyte poly(diallyldimethylammonium chloride) and AgNO3 in the presence of NaOH.

 

 

 

 

1270

 

Hydrothermal synthesis, characterization and acid catalytic activity of

nano Ce-La oxide powder

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yucai Hu*, Ping Yin, Tao Liang, Jiang Zhang & Dongdong Zhu

 

 

 

 

Ce-La oxide powder has been synthesized by hydrothermal method at 250°C using cerous nitrate, lanthanum nitrate and hydrazine hydrate as raw materials.La3+is embedded into the cubic crystal lattice of CeO2 and forms a homogeneous solid structure with particle diameter less than 50 nm. Ce-La oxide solid solution possesses higher acid catalytic performance and its catalytic mechanism is of the proton acid catalysis type.

 

 

 

 

 

 

1273

 

Synthesis and characterisation of a new Schiff base and its metal complexes

 

 

 

 

 

 

 

 

 

 

 

Gülnur Keser Karaoğlan*, Ulvi Avcıata & Ahmet Gül

 

 

 

 

A new Schiff base ligand, 2-(6-((E)-1-(2-heptadecylcarbonyl­oxyphenyl)methylideneamino) [1,10] phenanthrolin-5-yl-imino­methyl)phenyl stearate has been synthesised from the reaction of 5,6-bis(salicylideneimino)-1,10- phenanthroline with stearic acid. The ligand reacts with Co(II), Ni(II) and Cu(II) salts to form complexes.

 

 

1277

 

Preparation, crystal structure and thermal decomposition of phenylenediammonium dichloride salts

 

 

 

 

 

 

 

 

Inder Pal Singh Kapoor, Pratibha Srivastava, Gurdip Singh* & Roland Fröhlich

 

 

 

 

Phenylene-1,2-diammonium dichloride, phenylene-1,3-diammonium dichloride, phenylene-1,4-diammonium dichloride and 5-carboxyl-phenylene-1,3-diammonium dichloride salts have been prepared and characterized by elemental, spectral, gravimetric and X-ray crystallography. Thermal decomposition of these salts has been studied by TG and DSC and shows involvement of proton transfer as a primary step. Kinetic analysis of TG data has been evaluated by model fitting method and model free isoconversional methods.

 

 

1283

 

Preparation, crystal structure and microwave studies on ring-substituted arylammonium hydrogen sulfate salts

 

 

 

 

 

 

 

I P S Kapoor, Pratibha Srivastava, Gurdip Singh* & Roland Fröhlich

 

 

 

 

Three ring substituted arylammonium hydrogen sulfates/ring substituted dianilinium sulfates have been prepared from corresponding arylamines by treatment with excess conc. H2SO4 and characterized by X-ray crystallography, elemental, gravimetric and spectral analyses. The salts yield the corresponding ring substituted amino benzene sulfonic acids when subjected to microwave irradiation. It is observed that these salts undergo transformation to acid in solid state via proton transfer reaction prior to sulfonation.

 

 

Authors for correspondence are indicated by (*)


 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1221-1225

 

Synthesis, characterization and antimicrobial studies of Sb(III) complexes of substituted thioimines

Karuna Mahajan, Nighat Fahmi & Ran Vir Singh*

Received 17 August 2006; rerevised 24 June 2007

Some antimony complexes of a new class of substituted thioimines have been prepared by reacting Ph3Sb (III) with [1-(2-naphthyl) ethyledene] hydrazinecarbodithioic acid phenyl methyl ester (L1H), [1-(2-thienyl) ethyledene] hydrazinecarbodithioic acid phenyl methyl ester (L2H), [1-(2-pyridine) ethyledene] hydrazinecarbodithioic acid phenyl methyl ester (L3H) and [1-(2-furanyl)ethyledene] hydrazinecarbodithioic acid phenyl methyl ester (L4H), in unimolar and bimolar ratios using thermal as well as microwave method. All the new complexes have been characterized by elemental analyses, molecular weight determinations and spectral studies including electronic, IR, 1H and 13C NMR spectra. The spectral data are consistent with the tetra-coordinated and penta-coordinated environments around Sb(III). The bidentate ligands coordinate through the nitrogen and sulfur atoms. Free ligands and their metal complexes have been screened for their antimicrobial activity on different species of pathogenic fungi and bacteria and their biological activity is discussed briefly.

IPC Code: Int. Cl.8 C07F9/00

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1226-1232

 

Magnetic and spectral properties of adducts of copper(II) chlorobenzoates with substituted piperazines

B S Manhas, S B Kalia*, A K Sardana & K Lumba

Received 10 May 2006; revised 5 June 2007

Adducts of Cu(OOCR)2 (where R = 2-, 3- or 4-ClC6H4) with saturated substituted piperazines of the type Cu(OOCR)2(L-L)n [where n = 0.5 or 1 and L-L = 1-methylpiperazine (1-MePipz), 1,4-dimethylpiperazine (1,4-Me2Pipz), 2,6-dimethylpiperazine (2,6-Me2Pipz) and 1-phenylpiperazine (1-PhPipz)] have been prepared and characterized by elemental analysis, infrared, electronic reflectance, electron paramagnetic resonance spectral and magnetic moment studies. Three complexes which have room temperature magnetic moment values lower than the spin only values and have room temperature electron paramagnetic resonance spectra corresponding to S = 1, rather than S = 1/2, have been further subjected to magnetic susceptibility and electron paramagnetic resonance spectral measurements at different temperatures to evaluate spin-exchange parameter (-2J = 282-313 cm-1). Based upon the above studies, axially symmetric binuclear structure for complexes of the type Cu(OOCR)2(L-L), polymeric structure containing binuclear units for the Cu(OOCR)2(L-L)­0.5 complexes and axially symmetric polymeric square pyramidal or trans-pseudo octahedral structure for complexes of the type Cu(OOCR)2(2,6-Me2Pipz) (R = 2-, 3- and 4-ClC6H4), have been proposed.

IPC Code: Int. Cl.8 C07F1/08

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1233-1239

 

Magnetic and spectral studies on cobalt(II) chelates of a dithiocarbazate derived from isoniazid

S B Kalia*, K Lumba, G Kaushal & M Sharma

Received 17 January 2007; revised 6 July 2007

New cobalt(II) dithiocarbazates with different mononegative and dinegative counter anions, of the general formulae [Co(IN-DtczH)2]Xn (IN-DtczH = isonicotinoyldithiocarbazic acid; X = Cl, Br, NO3, ClO, CH3COO for n = 2 and X = SO4 and C2O4 for n = 1) for Zwitterionic complexes and [Co(IN-Dtcz)2] for a normal complex, have been obtained. These complexes have been investigated by elemental analyses, room-temperature infrared and electronic spectral and magnetic susceptibility measurements. Five of the complexes have also been investigated for variable temperature magnetic susceptibility measurements. The complexes, [Co(IN-DtczH)2]Xn (X = Cl, Br, NO3, ClO, CH3COO for n = 2; X = SO4 for n = 1) and [Co(IN-Dtcz)2] have NS linkage while the [Co(IN-DtczH)2]C2O4 complex has ONS bonded ligand. The magnetic and spectral studies suggest that [Co(IN-DtczH)2](NO3)2 is tetrahedral; [Co(IN-DtczH)2]X2 (X = Br, ClO4) and [Co(IN-Dtcz)2] are square planar; and, [Co(IN-DtczH)2]X2 (X = CH3COO, Cl) involves square planar-tetrahedral equilibrium. The [Co(IN-DtczH)2]X (X = SO4, C2O4) complexes have octahedral geometry with sulphato or oxalato bridged polymeric structure with appreciable superexchange antiferromagnetic interactions. The mononegative ions, i.e. nitrate, perchlorate and acetate are acting as counter anions.

IPC Code: Int. Cl.8 C07F15/06

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1240-1251

 

Homogeneous catalysis of aquachlororuthenium(III) complex and evaluation of individual kinetic and thermodynamic parameters of bromate-lactic acid redox reaction at low and high acid strengths

Ch Sanjeeva Reddy* & T Vijaya Kumar

Received 1 September 2006; revised 23 May 2007

Aquachlororuthenium(III) complex catalysed oxidation of lactic acid (LA) by bromate at low and high acid strengths has been studied and different reaction mechanisms have been proposed, depending on the composition of the mixture. At low acid strength, the reaction exhibits 1.0 order in [bromate], 0.13 order in [LA], 0.5 order in [catalyst] and a dualistic effect in [acid]. Primary kinetic isotope effect (kH/kD =1) has been found to be absent. However, an inverse solvent isotope effect (kD2O/kH2O = 0.75) is observed. The proposed mechanism involves oxidation of the formed Ru(III)-substrate complex by bromic acid, through complexation, to Ru(V)-substrate intermediate in the rate-determining step, which subsequently decomposes into CH3CHO and CO2 through C-C bond cleavage with regeneration of Ru(III) in the fast step. The same reaction at high acid strength exhibits first order each in [bromate] and [LA], 1.5 order in [catalyst], and an inverse fractional (-0.25) order in [acid]. The reaction also exhibits solvent isotope effect, while primary isotope effect is absent. The rate law is interpreted by a mechanism involving oxidation of Ru(III) to Ru(V) by Br(V) followed by the ternary complex formation between the formed Ru(V) and the preformed Ru(III)-substrate binary complex, which decomposes into products in the rate-determining step with regeneration of the catalyst. Spectroscopic data and the effects of dielectric constant and ionic strength are also in accordance with the mechanisms proposed. All the individual rate/formation constants involved in the mechanism proposed have been determined at different temperatures and their thermodynamic parameters have been evaluated and discussed.

IPC Code:Int. Cl.8 B01J8/00; C07B33/00

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1252-1256

 

Electrochemistry of [Fe4S4(SCH2CH2COO-)4]6- in liposomes and microemulsions

Raben Ch Roy, Diganta Kumar Das* & Biva Das

Received 18 August 2006: revised 16 May 2007

[Fe4S4(SCH2CH2COO-)4]6-, a structural analogue of active center of ferredoxin and P cluster of nitrogenase, shows two distinct reversible couples with redox potential values –643±5 mV and –972±5 mV vs. Ag-AgCl due to 3+/2+ and 2+/1+ couples of the core [Fe4S4] respectively in liposomes. Two redox linked protonation sites, with pKox at 3.2 with corresponding pKred at 4.3 due to carboxylate and another pKred at 5.8 due to thiopropionate S shift the redox potential of 3+/2+ couple by 200 mV. In microemulsion containing negative sds molecules (ME-sds) the redox potentials due to 3+/2+ and 2+/1+ couples are –670 mV and –920 mV (pH=4.6) while these values are –544 mV and –800 mV respectively (pH=5.5) versus Ag-AgCl in microemulsion containing positive ctab molecules (ME-ctab). The trend in diffusion co-efficient of the cluster in different medium is found to be: ME-sds>ME-ctab>lposomes.

IPC Code: Int. Cl8 C25B

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1257-1262

 

Ionic effects on some anticancer drugs from analysis of their metal ion and proton affinities

P K Bhattacharyya, Murshida Karim & C Medhi*

Received 8 September 2006; revised 25 June 2007

The proton affinities (PA) and the metal ion affinities (MA) of nitrogen mustards have been investigated to analyze the ionic effect in alkylation reactions. The ion affinities of N4 atomic site of nitrogen mustards are significant, and the proton affinities are more significant than the metal ion affinities. However, Na+ affinities are comparatively less than Mg2+ affinities. The values of ion affinities have been taken for comparing the ionic effect in alkylation reaction. The magnitudes of PA and MA (Mg2+) indirectly show the possibility of inhibitory effect at the intermediate state during aziridinium ion formation of alkylation reaction. So, the presence of H+ and Mg2+ may change the alkylation rate, since these ions acquire strong affinity for N4 of nitrogen mustards.

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1263-1265

 

Determination of acid dissociation constants of some monobasic organic acids in acetonitrile from molar conductance

Samik Nag & Dipankar Datta*

Received 21 April 2007; revised 5 July 2007

The pKa values of some 14 monobasic organic acids like carboxylates, phenols, etc. are determined in acetonitrile from conductivity measurements. These pKa values are found to be higher than those reported in the aqueous medium on the average by 2.8 (± 1.1) pKa unit. A thermodynamic rationalisation of this observation is provided. It emerges that an acid should be more acidic in water than in acetonitrile as water being more polar than acetonitrile brings about greater ionisation of an acid.

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1266-1269

 

Preparation of silver nanoparticles by heating a quaternary ammonium polyelectrolyte-AgNO3 aqueous solution in basic conditions

Yonglan Luo

Received 23 November 2006; revised 5 June 2007

Silver nanoparticles (~ 2 nm in size) have been prepared by heating an aqueous solution containing quaternary ammonium polyelectrolyte poly(diallyldimethylammonium chloride) and AgNO3 in the presence of NaOH. The formation of silver nanoparticles has been confirmed by UV-vis, TEM, and XPS data and the formation process traced by time-dependent UV-vis spectra. It is observed that addition of NaOH to the solution is crucial to the formation of silver nanoparticles.  

IPC Code: Int. Cl.8 B82B1/00

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1270-1272

 

Hydrothermal synthesis, characterization and acid catalytic activity of nano Ce-La oxide powder

Yucai Hu*, Ping Yin, Tao Liang, Jiang Zhang & Dangdong Zhu

Received 8 September 2006; revised 15 May 2007

Ce-La oxide powder has been synthesized by hydrothermal method at 250°C using cerous nitrate, lanthanum nitrate and hydrazine hydrate as raw materials and characterized by X-ray diffraction, transmission electron microscopy and infrared spectra. The acid catalytic performance of the sample has been investigated in the reaction of acetic acid and n-butyl alcohol. The results show that La3+ is embedded into the cubic crystal lattice of CeO2 and forms a homogeneous solid structure. The particle diameter of sample is less than 50 nm. Ce-La oxide solid solution possesses higher acid catalytic performance and its catalytic mechanism is of the proton acid catalysis type.

IPC Code: Int. Cl.8 B01J23/10; B01J37/00

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1273-1276

 

Synthesis and characterisation of a new Schiff base and its metal complexes

Gülnur Keser Karaoğlan*, Ulvi Avcıata & Ahmet Gül

Received 20 April 2006; revised 19 June 2007

A new Schiff base ligand, 2-(6-((E)-1-(2-heptadecylcarbonyl­oxyphenyl)methylideneamino) [1,10] phenanthrolin-5-yl-imino­methyl)phenyl stearate has been synthesised from the reaction of 5,6-bis(salicylideneimino)-1,10- phenanthroline with stearic acid. The ligand reacts with Co(II), Ni(II) and Cu(II) salts to form complexes. The ligand has been characterized by FTIR, 1H NMR (DMSO-d6), UV-vis and mass spectra, elemental analysis and fluorescence spectrophotometry. Protonation constants of the ligand and overall formation constants of the complexes have been calculated from potentiometric data using a computer program.

IPC Code: Int. Cl.8 C07F1/08; C07F15/04; C07F15/06

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1277-1282

 

Preparation, crystal structure and thermal decomposition of phenylenediammonium dichloride salts

Inder Pal Singh Kapoor, Pratibha Srivastava & Gurdip Singh*

Received 24 November 2006; revised 6 June 2007

Phenylene-1,2-diammonium dichloride (P-1,2-DADCl), phe­nylene-1,3-diammonium dichloride (P-1,3-DADCl), phenylene-1,4-diammonium dichloride (P-1,4-DADCl) and 5-carboxyl-phe­nylene-1,3-diammonium dichloride (5-carboxyl-P-1,3-DADCl) salts have been prepared and characterized by elemental, spectral, gravimetric and X-ray crystallography. Thermal decomposition of these salts has been studied by TG and DSC and shows involvement of proton transfer as a primary step. Kinetic analysis of TG data has been evaluated by model fitting method and model free isoconversional methods.

 

Indian Journal of Chemistry

Vol. 46A, August 2007, pp. 1283-1288

 

Preparation, crystal structure and microwave studies on ring-substituted arylammonium hydrogen sulfate salts

I P S.Kapoor, Pratibha Srivastava, Gurdip Singh, * & Roland Fröhlich

Received 15 January 2007; revised 13 July 2007

Three ring substituted arylammonium hydrogen sulfates (RSAHS)/ring substituted dianilinium sulfates (RDAS) have been prepared from corresponding arylamines by treatment with excess conc. H2SO4 and characterized by X-ray crystallography, elemental, gravimetric and spectral analyses. The RSAHS/RDAS salts yield the corresponding ring substituted amino benzene sulfonic acids (RSABSA) when subjected to microwave irradiation. It is observed that these salts undergo transformation to acid in solid state via proton transfer reaction prior to sulfonation.