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Indian Journal of Chemistry

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

 

VOLUME 43A

NUMBER 4

April 2004

 

CONTENTS

Papers

691

 Photo-induced DNA cleavage activity of ternary (N salicylidene-L methioninato)copper(II) complexes of phenanthroline bases

 

  

 

 

 

 

Anitha M Thomas, Anil D Naik, Munirathinum Nethaji & Akhil R Chakravarty*

 

Ternary (N-salicylidene-L-methioninato)copper(II) complexes containing planar heterocyclic bases show efficient light-induced DNA cleavage in absence of any external reagents by a mechanistic pathway involving formation of singlet oxygen as the reactive species.

 

 

 701

 Syntheses and 119Sn Mössbauer spectral characterization of tin(IV) complexes of 4-acyl-1-phenyl-3 methylpyrazolones-5 and molecular modelling of 4-acetyl-1-phenyl-3-methyl-pyrazolone-5

 

Bieluonwu A Uzoukwu*, Karsten Gloe, Michael Menzel & Kamila Wawrzyniak

 

 

 

 

706

 

On the nature of noble metal electrodes prepared using formaldehyde as reducing agent

 

B Viswanathan*, V Chidambaram & S Chandravadanam

 

 

The noble metal electrodes used in fuel cells have many active sites in addition to the zero valent states. Other metals added like Ru have other roles to play in addition to removing the poisoning effects due to intermediate CO in the oxidation of methanol.

 710

 Electrical, magnetic and catalytic oxidation studies on LaMn1-XCoXO3 system

  

A V Salker* & Teotone Vaz

 

Lanthanum manganates and cobaltates and their intermediate compositions LaMn1-XCoXO3 (x = 0.0, 0.3, 0.5, 0.7 and 1.0) with a perovskite structure, synthesized by co-precipitation precursor technique, show phase transitions from semi-conductor to semi-metallic in the range of 570-630 K and also considerable increase in activity of carbon monoxide oxidation to carbon dioxide.

715

Effect of tetraalkylammonium bromides on the micellar behavior of ionic and nonionic surfactants.

   

Jay Patel, Dharmesh Varade* & Pratap Bahadur

 

Effect of tetraalkylammonium bromides (methyl, ethyl, n-propyl and n-butyl) on the surface activity and micellar behavior of sodium dodecyl sulfate, tetradecyl trimethyl- ammonium bromide and dodecyl decapolyethylene glycol ether has been examined by surface tension, dye solubilization, viscosity and cloud point measurements. The results are discussed in the light of charge and hydrophobicity of tetraalkylammonium salts.

 

 722

 Excess molar volumes and viscosities of binary liquid mixtures of n-alkoxyethano1 + 1-propanol systems at 298.15, 308.15 and 318.15 K

 

Amalendu Pal* & Anil Kumar

 

 Excess molar volumes and viscosities for binary liquid mixtures of n-alkoxyethano1s + 1-propanol have been measured as a function of composition at 308.15 and 318.15 K and atmospheric pressure over the full range of composition. The excess volumes and viscosity deviations have been correlated using the Redlich –Kister polynomial equation.

 

 730

 Ultrasonic, viscometric and volumetric studies of some bioapplicable systems involving ZnCl2, dextrose and methionine in water

   

A P Mishra

 

 Ultrasonic velocity, density, refractive index and viscosity of dextrose + methionine, ZnCl2 + dextrose, ZnCl2 + methionine and ZnCl2 + methionine + dextrose in water have been determined and apparent molar volume, partial molar volume, experimental slope, adiabatic compressibility, apparent molar compressibility, viscosity coefficients A and B of Jones-Dole equation have been calculated at 298.15 K and discussed.

734

Conductance study of electrolyte solutions in binary mixtures of dimethylformamide and dimethylsulphoxide at different temperatures

 

M S Chauhan*, G Kumar, S Chauhan & S Gupta

 

Limiting molar conductances  of Ph4PBPh4, Bu4NBPh4, Bu4NNO3, Bu4NClO4, Bu4NBr, Bu4NI, Ph4PBr, NaBPh4, AgClO4, AgNO3, LiNO3, NaNO3, KNO3 and NaBr have been reported in DMF – DMSO mixtures at 25, 35 and 45 oC. The results indicate the existence of electrostatic ion – solvent interactions in the case of alkali metal cations via O atom of both the solvents and specific interactions between Ag+ ion and DMSO via S atom of S=O group of DMSO molecule.

Notes

739

Experimental studies on BZ reaction system containing oxalic acid and acetone as mixed organic substrate in a CSTR

  

C Basavaraja, V R Kulkarni*, S Mohan, Y M Iyer & G V Subba Rao

 

 Belousov-Zhabotinskii reaction containing bromate-CeIV-H2SO4-mixed organic substrate (oxalic acid and acetone) has been studied in a continuously stirred tank reactor. Flow rate and inflow concentration show lower and upper limits for the appearance/ disappearance  of oscillating behaviour.

 743

A new approach to collision factor theory applied to binary and ternary liquid mixtures at different temperatures

 

Rita Mehra* & Rekha Israni

 

 Ultrasound velocities have been measured  in pure hexadecane, heptadecane, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and in some binary and ternary mixtures and these values have been compared with those predicted on the basis of collision factor theory. A new approach, incorporating collision volume instead of molar volume, has been applied.

748

 Physico chemical studies on complexation between b–cyclodextrin and cationic surfactants

 

Xilian Wei, Qing Sang, Baolin Yin & Dezhi Sun*

 

 Inclusion complexation of b-cyclodextrin with a homologue of new cationic surfactants, 3-alkoxyl-2-hydroxylpropyl trimethyl ammonium chlorides in aqueous solution have been studied using surface tension measurements at different temperatures. Results indicate the host-guest inclusion to be a spontaneous, enthalpy – entropy compensational process.

 

 752

Ultrasonic study of  molecular interactions in ternary mixtures of  o-chlorophenol (1) + acetonitrile (2) + methanol, N,N- dimethyl -formamide,  isobutyl alcohol (3) at 303.15K

  

G V RamaRao,  A Viswanatha Sarma & C Rambabu*

 

The ultrasonic velocity and density have been measured for o-chlorophenol (1)+acetonitrile (2) + methanol (3), N-N-dimethylformamide (3), isobutyl alcohol (3) at 303.15 K over the entire range of composition. Adiabatic compressibility, intermolecular free length, molar volume and acoustic impedance have been obtained for all the mixtures.

 756

Quantitative correlation between log K of the complexes and CA, EA and DA parameters of the metal ions/ lewis acids

 

B L Gorsi*, Meenal Vig & Sushila Dhaka

 

Regression analysis reveals a significant linear correlation  of the formation constants of the complexes and ionic tendencies (EA),covalent tendencies (CA) and dissolvation effect (steric hindrance DA) of the metal ions/lewis acids with different ligands in aqueous solution.

 760

A dinuclear copper(II) complex based on bridging oxalate and single dicyanamide

 

Partha Sarathi Mukherjee, Sanjit Konar, Sudipta Dalai, Ennio Zangrando & Nirmalendu Ray Chaudhuri*

 

 

 763

Synthesis, magnetic and spectral studies of some novel binuclear dioxomolybdenum(VI) chelates involving Schiff bases derived from sulpha drugs and 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-
5-one

 

R C Maurya*, A Pandey  & D Sutradhar

 

 

769

Studies on organomercury(II) complexes with piperidine and 2-aminopyridine dithiocarbamates

 

Rama Sharma & N K Kaushik*

 

 

 

773

Synthesis and characterization of some vanadium(III) complexes with tetradentate schiff bases

  

Kamalendu Dey*, Bijali Bikash Bhaumik & Saikat Sarkar

 

              

 778

Synthesis of new bis(2,4-pentanedionato)-zirconium(IV) aryloxides and their thermal studies

 

S S Bhatt*, Raj Kumari, Neeraj Sharma & S C Chaudhry

 

Bis(2,4-pentanedionato)zirconium(IV) aryloxides with the composition ZrCl2-n(acac)2(OAr-X)n (where n= 1 or 2; acac = 2,4-pentanedionato anion; OAr-X = OC6H3Cl2-2,6; OC6H3Cl2-2,4 and OC6H2Cl3-2,4,6) have been synthesized.  Replacement of chlorides of ZrCl2(acac)2 by phenoxide/aryloxide ligands lowers the decomposition temperature of the complexes indicating their potential use as new and better precursors for making thin films of ZrO2.

782

Synthesis and characterization of a new vic-dioxime ligand and its complexes with cobalt(II), nickel(II) and copper(II)

 

Nebahat Demirhan*, Ibrahim Erden & Ulvi Avciata

 

 786

Synthesis, spectral characterisation and redox properties of heteroleptic ruthenium(II)-p-tolylazoimidazole-pyridine complexes

 

P Byabartta, Sk Jasimuddin & C Sinha*

 

790

 Synthesis, characterisation and electrochemistry of [Ru(L)(2,2¢-bpy)Cl2]: (L= 4 aryl substituted thiosemicarbazide; bpy = bipyridine)

 

Milan Maji*, Parbati Senguptaa & Rupam Dindaa

 

 793

 Synthesis and characterization of novel N-functionalized macrocyclic dioxotetraamines bearing 8-hydroxyquinoline and its metal complexes: Stability in aqueous solutions

  

Xiaojun Zhao*, Xuncheng Su, Encui Yang, Ying Wang, Huakuan Lin*, Shourang Zhu & Hongwei Sun

 

 

                    

 799

Outer-sphere electron transfer from platinum(II) to Keggin-type 12-tungstocobaltate(III) in the presence and absence of chloride ions

 

 B D Bhosale & G S Gokavi*

 

The reaction between Pt(II) and [CoIIIW12O40]5- proceeds with two, one-electron steps involving formation of unstable Pt(III) followed by its reaction with another oxidant. The reaction rate is unaffected by the [H+], whereas chloride ion accelerates the reaction. The reaction follows chloride independent and dependent paths leading to a two term rate law,
rate = {k1 + Kk2 [Cl-]} [Pt(II)] [CoIIIW12O40]5.

Authors for correspondence are indicated by (*)

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 691-700

 

Photo-induced DNA cleavage activity of ternary
(N-salicylidene-l-methioninato)copper(II) complexes of phenanthroline bases

Anitha M Thomas, Anil D Naik, Munirathinum Nethaji & Akhil R Chakravarty*

 

Copper(II) complexes [Cu(salmet)B] (1-3), where H2salmet is the Schiff base derived from salicylaldehyde and l-methionine and B is heterocyclic bases like 1,10-phenanthroline (phen, 1), dipyridoquinoxaline (dpq, 2) and dipyridophenazine (dppz, 3), are prepared and their DNA cleavage properties studied. Complex [Cu(tBu2salmet)(phen)].CHCl3 (4.CHCl3) has been prepared for structural characterization using single crystal X-ray crystallography. Complex 4 has a ternary structure in which the copper displays a distorted square pyramidal (4 + 1) geometry showing tri- and bidentate mode of bonding for the Schiff base and phen, respectively, in CuN3O2 coordination. The phen ligand exhibits axial-equatorial mode of bonding, while the dianionic Schiff base binds at the equatorial sites of the basal plane. The one-electron paramagnetic complexes show a d-d band in the electronic spectra in DMF at ca. 670 nm and axial EPR spectral features indicating {dx2-y2}1 ground state in a DMF glass at 77 K. The complexes are redox active displaying quasi-reversible cyclic voltammetric response near 0.1 V (vs. SCE) in DMF-0.1 M TBAP assignable to the Cu(II)/Cu(I) couple. The complexes bind to the calf thymus DNA but to a lesser extent in comparison to bis(phen)copper(II) species that has been used as a standard. The complexes cleave supercoiled (SC) pUC19 DNA in dark under aerobic conditions by oxidative process in presence of mercaptopropionic acid as a reducing agent. They also show photo-induced DNA cleavage on irradiation with UV light of 312 nm or visible green light of 532 nm. The cleavage activity follows the order: 3 ~ 2 > 1. The mechanistic pathways for the DNA cleavage reactions are discussed.

 

IPC Code: Int.Cl.7 C01G 3/00; A61P 35/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 701-705

 

Syntheses and 119Sn Mössbauer spectral characterization of tin(IV) complexes of 4-acyl-1-phenyl-3 methylpyrazolones-5 and molecular modelling of 4-acetyl-1 phenyl-3-methylpyrazolone-5

 Bieluonwu A. Uzoukwu*, Karsten Gloe, Michael Menzel & Kamila Wawrzyniak

 

The syntheses of tin(IV) complexes of 4-acetyl, 4-propanoyl and 4-butanoyl derivatives of 1-phenyl-3-methylpyrazolone and 4-adipoyl and 4-sebacoyl derivatives of bis(1-phenyl-3-methylpyrazolone-5) have been carried out. The complexes have been characterized by elemental analyses, UV, IR, 1H NMR and 119Sn Mössbauer spectral studies. The complexes conform to the general formula L2SnCl2 and XSnCl2.H2O where L is 4-acyl-1-phenyl-3-methyl-pyrazolonate anion and X is 4-acylbis(1-phenyl-3-methylpyrazolonate) dianion. Results from 119Sn Mössbauer spectral studies show that the complexes are cis-dichloro complexes with octahedral configuration. The molecular structure of 4-acetyl-1-phenyl-3-methylpyrazolone-5 has been determined using the molecular modelling HyperChem™ program. It shows that the acetylpyrazolone chelate ring is planar with the phenyl ring twisted by 36° from the pyrazolone plane.

 

IPC Code: Int.Cl.7 C07D 231/00; C07F 7/22; C01J 3/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 706-709

 

On the nature of noble metal electrodes prepared using formaldehyde as reducing agent

B Viswanathan*, V Chidambaram & S Chandravadanam

 

The noble metal electrodes used in fuel cells have many active sites in addition to the zero valent states. The other metals added like Ru have other roles to play in addition to removing the poisoning effects due to intermediate CO in the oxidation of methanol. The advantages of using formaldehyde for reduction of noble metal ions in relation to hydrogen reduction method are also given.

 

IPC Code: Int.Cl.7 H01M 4/92

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 710-714

 

Electrical, magnetic and catalytic oxidation studies on LaMn1-XCoXO3 system

A V Salker* & Teotone Vaz

 

Lanthanum manganates and cobaltates and their intermediate compositions LaMn1-XCoXO3 (x = 0.0, 0.3, 0.5, 0.7 and 1.0) with a perovskite structure have been synthesized by co-precipitation precursor technique. These compounds show phase transitions from semi-conductor to semi-metallic in the range of 570-630 K and also considerable increase in activity of carbon monoxide oxidation to carbon dioxide. An attempt has been made to understand the effect of B-site substitution in the lattice of LaMnO3 and their correlation with the solid-state properties.

 

IPC Code: Int.Cl.7 B01J 23/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 715-721

 

Effect of tetraalkylammonium bromides on the micellar behaviour of ionic and non-ionic surfactants

Jay Patel, Dharmesh Varade* & Pratap Bahadur

 

Effect of tetraalkylammonium bromides (methyl, ethyl, n-propyl and n-butyl) on the surface activity and micellar behaviour of sodium dodecyl sulfate (NaDS), tetradecyltrimethylammonium bromide (C14TABr) and dodecyl decapolyethylene glycol ether (C12E10) has been examined by surface tension, dye solubilization, viscosity and cloud point measurements. Strong decrease in critical micelle concentration (CMC) and increase in solubilization power has been observed for NaDS; the effect is more with longer tetraalkyl salts. These salts also decrease the CMCs of C14TABr, while the CMCs of C12E10 remain practically unaffected even up to 0.1 M concentration. However, cloud point (CP) of C12E10 increases in the presence of these salts except in tetramethylammonium bromide where it decreases above 0.05 M. Viscosity results indicate the micellar growth for NaDS and tetrabutylammonium bromide. The micellar solution of NaDS exhibits a cloud point phenomenon in the presence of tetrabutylammonium bromide. The results are discussed in the light of charge and hydrophobicity of tetraalkylammonium salts.

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 722-729

 

Excess molar volumes and viscosities of binary liquid mixtures
of n-alkoxyethano1 + 1-propanol systems at
298.15, 308.15 and 318.15 K

Amalendu Pal* & Anil Kumar

 

Excess molar volumes and viscosities for binary liquid mixtures of n-alkoxyethano1s + 1-propanol have been measured as a function of composition at 308.15 and 318.15 K and atmospheric pressure over the full range of composition. Excess molar volume and viscosity at 298.15 K for the mixtures, 1-propanol + diethylene glycol monobutyl ether (2-(2-butoxyethoxy) ethanol), C4H9(OC2H4)2OH and viscosity at 298.15 K for the mixtures, 1-propanol + diethylene glycol monoethyl ether (2-(2-ethoxyethoxy) ethanol), C2H5(OC2H4)2OH have also been measured over the whole composition range. From these results deviation in viscosity, Dh, from a mole fraction average have been calculated at various temperatures. The excess volumes and viscosity deviations have been correlated using the Redlich-Kister polynomial equation by the method of least-squares for the estimation the adjustable parameters and the standard errors. McAllister’s three body and four body interaction models are used to correlate the kinematic viscosities. Furthermore, activation enthalpies, DH* and entropies, DS* of viscous flow have been evaluated and their variation with concentration discussed.

 

IPC Code: Int.Cl.7 G01N

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 730-733

 

Ultrasonic, viscometric and volumetric studies of
some bioapplicable systems involving ZnCl2, dextrose
and methionine in water

 A P Mishra

 

Ultrasonic velocity, density, refractive index and viscosity of dextrose + methionine, ZnCl2 + dextrose, ZnCl2 + methionine and ZnCl2 + methionine + dextrose in water have been determined. From these measured values, the apparent molar volume (fV), partial molar volume (fV0), experimental slope (SV), adiabatic compressibility (bS), apparent molar compressibility (fK), viscosity coefficients A and B of Jones-Dole equation, have been calculated at 298.15 K. The observed and calculated values have been used to explain molecular association, ion-solvent and hydrogen bonding interaction. The above study may be helpful in understanding the dynamics between metal ions and biomolecules.

 

IPC Code: Int.Cl.7 G01N; C01G 9/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 734-738

 

Conductance study of electrolyte solutions in binary mixtures of dimethylformamide and dimethylsulphoxide at
different temperatures

 M S Chauhan*, G Kumar, S Chauhan & S Gupta

 

Limiting molar conductances (Lo) of Ph4PBPh4, Bu4NBPh4, Bu4NNO3, Bu4NClO4, Bu4NBr, Bu4NI, Ph4PBr, NaBPh4, AgClO4, AgNO3, LiNO3, NaNO3, KNO3 and NaBr have been determined in DMF-DMSO mixtures at 25, 35 and 45°C using Shedlovsky conductance equation. Limiting molar ionic conductances (loi) have been calculated from lo(Ph4P+) @ lo(Ph4B-) assumption. Discussion of effective ionic radii (ri) calculated from lio values is based on ion-solvent interactions. The results indicate the existence of electrostatic ion-solvent interactions in the case of alkali metal cations via O atom of both the solvents and specific interactions between Ag+ ion and DMSO via S atom of S=O group of DMSO molecule. The latter is found to be in agreement with the concept of soft acid-base type of interactions. Association constants (KA), however, yield no significant contribution.

 

IPC Code: Int. Cl.7 G01N

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 739-742

 

Experimental studies on BZ reaction system
containing oxalic acid and acetone as mixed organic substrate in a CSTR

C Basavaraja, V R Kulkarni*, S Mohan, Y M Iyer & G V Subba Rao

 

Belousov-Zhabotinskii reaction containing Bromate-CeIV-H2SO4-mixed organic substrate (oxalic acid and acetone) has been studied in a continuously stirred tank reactor. The behaviour with respect to flow rate and inflow concentrations has been investigated using platinum as the indicator electrode. Each of these variables show lower and upper limits for the appearance/disappearance of oscillating behaviour. These observations have been discussed with reference to model simulations. Necessity for modification of the model to account for discrepancies is indicated.

 

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 743-747

 

A new approach to collision factor theory applied to binary and ternary liquid mixtures at different temperatures

 Rita Mehra* & Rekha Israni

 

Ultrasound velocities have been measured in pure hexadecane, heptadecane, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol and in the binary mixtures of hexadecane/heptadecane with 1-alkanols at 298.15, 308.15 and 318.15 K. Similarly ultrasonic velocity has also been measured for the ternary systems of hexadecane +1-butanol and hexadecane + 1-heptanol with dimethyl sulphoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF) each as a third component at three temperatures. The experimental values of ultrasonic velocities have been compared with those predicted on the basis of collision factor theory and the demerits of this theory have been overcome by applying a new approach incorporating collision volume instead of molar volume and the number of molecules involved in collisions. This modification has also been applied on the systems studied by other workers and the relative merits have been discussed. Further, the effect of temperature provides an opportunity to study the nature and extent of interactions between component molecules as interactions are a result of active collisions between molecules.

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 748-751

 

Physico chemical studies on complexation between
b–cyclodextrin and cationic surfactants

Xilian Wei, Qing Sang, Baolin Yin, & Dezhi Sun*

 

Inclusion complexation of b-cyclodextrin (b-CD) with a homologue of new cationic surfactants, 3-alkoxyl-2-hydroxylpropyl trimethyl ammonium chlorides (RmTAC) in aqueous solution have been studied using surface tension measurements at different temperatures. The binding constants of 1:1 complexes have been calculated and important thermodynamic parameters of the inclusion processes are estimated using fundamental thermodynamic equations. Standard change of Gibbs free energy DcGm° of every complex process is negative, which indicates that the host-guest inclusion is a spontaneous process. All the values of standard changes of enthalpy and entropy, DcHm° and DcSm° are positive, which shows that the inclusion process is enthalpy-entropy compensational one. However, the entropy effect, TDcSm° is quite evidently larger than the heat effect, DcHm°, which indicates that the inclusion coordination between b-CD and RmTAC is also entropy driven process, as well as an endoergic driven process.

 

IPC Code: Int. Cl.7 G01N

 

 

 

Indian Journal of Chemistry

 Vol. 43A, April 2004, pp. 752-755

 

Ultrasonic study of molecular interactions in ternary mixtures of o-chlorophenol (1) + acetonitrile (2) + methanol, N,N-dimethylformamide, isobutyl alcohol (3) at 303.15 K

G V Rama Rao, A Viswanatha Sarma & C Rambabu*

 

The ultrasonic velocity and density have been measured for o-chlorophenol (1)+acetonitrile (2) + methanol, N-N-dimethy-l formamide or, isobutyl alcohol (3) at 303.15 K over the entire range of composition. The thermodynamic parameters such as adiabatic compressibility, intermolecular free length, molar volume and acoustic impedance have been obtained for all mixtures from experimental data with a view to investigating the exact nature of the molecular interaction. The excess values of the said parameter have also been calculated. The deviation from ideality of these parameters is explained on the basis of molecular interactions between the constituent components of the mixture.

 

IPC Code: Int. Cl.7 G01N

 

 

 

Indian Journal of Chemistry

 Vol. 43A, April 2004, pp. 756-759

 

Quantitative correlation between logK of the complexes and CA, EA and DA parameters of the metal ions/lewis acids

 B L Gorsi*, Meenal Vig & Sushila Dhaka

 

Regression analysis reveals a significant linear correlation of the formation constants of the complexes and ionic tendencies (EA), covalent tendencies (CA) and dissolvation effect (steric hindrance DA) of the metal ions/lewis acids with different ligands in aqueous solution. As a result of the regression analysis, the predictive equations are much promising and stability constant values have been obtained for these ligands with any metal ion with certain accuracy.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, April 2004, pp. 760-762

 

A dinuclear copper(II) complex based on bridging oxalate and single dicyanamide

Partha Sarathi Mukherjee, Sanjit Konar, Sudipta Dalai, Ennio Zangrando &

Nirmalendu Ray Chaudhuri*

 

A discrete dinuclear species [Cu2(dca)(ox)(tmen)2](ClO4) [dca = dicyanamide, ox = oxalate and tmen = N,N,N¢,N¢- tetramethylethane-1,2-diamine] representing a rare example of a complex having bridging oxalate and single dicyanamide between two metal centres, has been synthesised and characterised by X-ray single crystal structure determination and low temperature magnetic measurements.

 

IPC Code: Int. Cl.7 C07F 1/08; G01N 23/20

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 763-768

 

Synthesis, magnetic and spectral studies of some
novel binuclear dioxomolybdenum(VI) chelates involving Schiff bases derived from sulpha drugs and
4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one

R C Maurya*, A Pandey  & D Sutradhar

 

This paper reports the synthesis of six new binuclear dioxomolybdenum(VI) complexes of the composition [{MoO2(OH)2}2(L)2], where L = N-(4'-benzoylidene-3'-methyl-1'-phenyl-2'-pyrazoline-5'-one)sulphamethoxazole (HL1), N-(4'-benzoylidene- 3' -methyl-1'-phenyl-2'-pyrazoline-5'-one)sulphadi­mi­dine (HL2), N-(4'-benzoylidene-3'-methyl-1'-phenyl-2'-pyrazoline-5'-one)sulphadiazine (HL3); N-(4'-benzoylidene-3'-methyl-1'-phenyl-2'-pyrazoline-5'-ne)-sulphanilamide (HL4), N-(4'-benzoylidene-3'-methyl-1'-phenyl-2'-pyrazoline-5'-) sulphame­razine (HL5) or N-(4'-benzoylidene-3'-methyl-1'-phenyl-2'-pyrazoline-5'-one)sulphadimethoxine (HL6). These complexes have been obtained by the interaction of bis(acetylacetonato)­dioxomolybdenum(VI) with the said ligands in ethanol. All these complexes have been characterized by elemental analysis, molar conductance, decomposition temperature and magnetic measurements, 1HNMR, IR and electronic spectral studies.

 

IPC Code: Int. Cl.7  C01G 39/2

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 769-772

 

Studies on organomercury(II) complexes with piperidine and 2-aminopyridine dithiocarbamates

 Rama Sharma & N K Kaushik*

 

The complexes of organomercury (II) chloride [RHgCl, where R=C6H5 (phenyl), p-Cl C6H4 (p-chlorophenyl), p-Br C6H4 (p-bromophenyl), o-, p-HOC6H4, (o-, p-hydroxyphenyl) with piperidine dithiocarbamate (L1) and 2-aminopyridine dithiocarbamate (L2) have been synthesized and characterised by IR, UV and 1H NMR spectral studies. Conductance measurement reveals that the compounds are non electrolytes. Thermogravimetric (TG) and differential thermal analysis (DTA) curves and their variations have been correlated with some structural parameters of the complexes. Activity of all the complexes vs. E. Coli, Z. mobilis bacterial strains and activity vs. A.niger, Cerveleria fungal strians have been studied and the general order of activity has been deduced.

 

IPC Code: Int.Cl.7 C01G 13/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 773-777

 

Synthesis and characterization of some vanadium(III) complexes with tetradentate schiff bases

Kamalendu Dey*, Bijali Bikash Bhaumik & Saikat Sarkar

 

A series of vanadium(III) mixed ligand complexes of biological interest have been synthesized. The complexes correspond to the general formula [V(Lig)XY], where ‘Lig’ means the dianion of different potentially quadridentate schiff bases and X = Clor Br while Y = Py or thf. The newly synthesized compounds have been characterized by elemental analyses, molar conductances, magnetic moment values, molecular weights and spectroscopic (IR, UV-vis) data. A pseudo octahedral geometry around vanadium(III) has been proposed on the basis of magnetic and spectral studies.

 

IPC Code: Int.Cl.7 C01G31/00; C07C 251/02

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 778-781

 

Synthesis of new bis(2,4-pentanedionato)-zirconium(IV) aryloxides and their thermal studies

S S Bhatt*, Raj Kumari, Neeraj Sharma & S C Chaudhry

 

Bis(2,4-pentanedionato)zirconium(IV) aryloxides with the composition ZrCl2-n(acac)2(OAr-X)n (where n = 1 or 2; acac = 2,4-pentanedionato anion; OAr-X = OC6H3Cl2-2,6; OC6H3Cl2-2,4 and OC6H2Cl3-2,4,6) have been synthesized by reacting ZrCl2(acac)2 and Me3SiOAr-X in predetermined molar ratios in toluene under reflux. These complexes have been characterized by physico-chemical techniques such as elemental analysis, IR, 1H NMR, TGA/DTA, molecular weight determinations and molar conductance measurements. The mechanism and kinetic parameters (DE* and A) of non-isothermal decomposition have been evaluated from TG curves of the complexes using Coats-Redfern equation. A considerable decrease in the FDTs of the complexes in the TG curves indicate then potential use as precursors in making thin films of ZrO2.

 

IPC Code: Int.Cl.7 C01G 25/02

 

 

 

Indian Journal of Chemistry

 Vol. 43A, April 2004, pp. 782-785

 

Synthesis and characterization of a new vic-dioxime ligand and its complexes with cobalt(II), nickel(II) and copper(II)

 Nebahat Demirhan*, İbrahim Erden & Ulvi Avcıata

 

A new vic-dioxime ligand (LH4), 1,10-phenanthrolino-5,6-bis(2,3-dihyroxyimino-1-aza) propane has been synthesized from the reaction of 5,6-diamino-1,10-phenanthroline with anti-chloromethylglyoxime. The ligand reacts with Co(II), Ni(II) and Cu(II) salts to form complexes. The complexes have been characterized by FTIR, 1H NMR (DMSO-d6), elemental analyses and magnetic measurements. Protonation constants of the ligand and overall formation constants of the complexes have been calculated from potentiometric data using the program TITFIT.

 

IPC Code: Int.Cl.7 C01G 51/00, C01G 3/00, C01G 53/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, April 2004, pp. 786-789

 

Synthesis, spectral characterisation and
redox  properties of heteroleptic ruthenium(II)–p-tolylazoimidazole–pyridine complexes

P Byabartta, Sk Jasimuddin & C Sinha*

 

Five heteroleptic ruthenium(II) complexes of formulae [Ru(RPy)2(MeaaiMe)2](ClO4)2.H2O (1-5) (MeaaiMe = p-Me-C6H4-N=N-C3H2, RPy: R = H (Pyridine, 1), o-Me (o-methylpyridine, 2), p-Me (p-methylpyridine, 3), p-NMe2 (p-N,N-dimethylpyridine, 4), p-Cl (p-chloropyridine, 5) have been synthesized from ctc-[RuCl2(MeaaiMe)2] + AgNO3 and RPy. The complexes are characterized by IR, UV-Vis and 1H-NMR spectral data. They exhibit high intense MLCT transition in 520-545 nm. Cyclic voltammogram shows Ru(III)–Ru(II) couple alongwith ligand reductions.

 

IPC Code: Int. Cl.7  C01G 55/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, April 2004, pp. 790-792

 

Synthesis, characterization and electrochemistry of [Ru(L)(2,2¢-bpy)Cl2]: (L= 4 aryl substituted thiosemicarbazide; bpy = bipyridine)

 Milan Maji*, Parbati Sengupta, & Rupam Dinda*

 

A series of ruthenium (II) complexes of general formula Ru(L)(bipy)Cl2 with different thiosemicarbazides (L) which ligated to the metal ion in the thione form have been synthesized by reacting Ru(bipy)Cl4 with the corresponding ligands in methanol. One bipyridine molecule and two chloride ligands complete the hexacoordination. The compounds have been characterised by elemental analysis, magnetic moment measurement and by different spectroscopic methods. The redox behaviour of the compounds has been explored by cyclic voltammetry.

 

IPC Code: Int.Cl.7 C01G 55/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 793-798

 

Synthesis and characterization of novel N-functionalized macrocyclic dioxotetraamines bearing 8-hydroxyquinoline and its metal complexes: Stability in aqueous solutions

 Xiaojun Zhao*a,b, Xuncheng Sua, Encui Yangb, Ying Wangb, Huakuan Lin*a,

Shourang Zhu & Hongwei Sun

 

Novel 4-(5¢-8¢-hydroxyquinoline)methylene-1,4,7,10-tetraaza-cyclotridecane–11,13-dione ligand (L) has been synthesized by simple method, and characterized by elemental analyses, IR and 1H NMR. It has two chelating sites each able to react with a transition metal ion to form complexes. At 25.0±0.1°C, I = 0.1 mol/dm3 NaNO3, potentiometric titrations have been performed to determine the protonation of L-5-R-1,10-phenanthroline-Cu(II) (R = CH3, H, Cl, NO2) and the stability constants of Cu(II) and Co(II). The results show that for Cu(II) and Co(II) complexes, 8-hydroxyquinoline is a stronger chelating reagent than tetra-amine[13]ene macrocycles. Molecular mechanics (MM+) calculations have been performed to assess the stability of ternary mixed system on Co(II)-l-5-substituted-1,10-phenanthroline-Cu(II) and Cu(II)-l-5-substituted-1,10-phenanthroline-Cu(II). The coordination ability for different coordination sites and for different metal ions (Co(II) and Cu(II)) at the same sites have been compared. The calculated results agree with those obtained experimentally.

 

IPC Code: Int.Cl.7 C07F 1/08; C07F 15/06

 

 

 

Indian Journal of Chemistry

Vol. 43A, April 2004, pp. 799-802

 

Outer-sphere electron transfer from platinum(II) to
Keggin-type 12-tungstocobaltate(III) in the presence and absence of chloride ions

B D Bhosale & G S Gokavi*

 

The reaction between Pt(II) and [CoIIIW12O40]5- proceeds with two, one-electron steps involving formation of unstable Pt(III) followed by its reaction with another oxidant. The reaction rate is unaffected by the [H+] as there are no protonation equlibria involved with both the reactants whereas, chloride ion accelerates the reaction and the reaction follows chloride independent and dependent paths leading to a two term rate law, rate= {k1 + Kk2 [Cl-]} [Pt(II)] [CoIIIW12O40]5-. The chloride ion dependent path is due to rapid substitution of chloride ion on PtCl42-. The products formed have been found to be PtCl4(aq) and PtCl62- in the absence and presence of chloride ion respectively. Increase in the ionic strength and decrease in the relative permittivity of the medium increase the rate of the reaction. This is due to the formation of an outer-sphere complex between the two reactants. The activation parameters in the presence and absence of chloride ions have also been determined and the values support the proposed mechanism.

 

IPC Code: Int. Cl.7 CO1G 55/00; CO1 G 41/00; CO1 G 51/00