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Indian Journal of Chemistry

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

 

 

VOLUME 43A

NUMBER 9

SEPTEMBER 2004

 

 

CONTENTS

 
Papers

 1815

 

A quantum mechanical localized molecular orbital study of the physical process of the planar (D3h) to pyramidal (C3v) structural reorganization of trifluoro methyl cation

 

 

 Dulal C Ghosh & Arindam Chakraborty

 

 (D3h)                                 (T.S)                         (C3v)

Acceptor  Donor                                        Super molecule

Sub-Systems

 1824

 Semi-empirical calculation of the transport properties of the CH4-noble gas mixtures from the interaction potential energy function using the inversion method

 

Behzad Haghighi*, Mohammad Fathabadi & Mohammad Mehdi Papari

 

 Viscosity, diffusion coefficients, and thermal diffusion factors for five equimolar binary gas mixtures of CH4-noble gases have been determined from the principle of corresponding states of viscosity by the inversion technique. The interaction potential energies from the inversion procedure reproduce viscosities within 1%, diffusion coefficients within 5%, and thermal diffusion factors within 25%.

 1832

Triplet state characteristics of IR laser dyes: A pulse radiolysis study

 

 

 

 

M Rele, A K Singh, D Palit & T Mukherjee*

 

 The triplet-triplet (T-T) absorption spectra and decay characteristics have been investigated for four IR laser dyes, namely, IR-140, IR-144, Q-Switch 1 and Q-Switch 5. Triplet state characteristics of these IR dyes have been measured. Using various triplet donors and acceptors, the triplet energy levels of these dyes have been estimated.

1838

Studies of Ti0.5Zr0.5O2  supported CuO catalysts for NO + CO reaction

 

 

 

Guang-hui Ding, Xiao-yuan Jiang, Yue-juan Wang & Xiao-ming Zheng

 

The activities of CuO supported on Ti0.5Zr0.5O2 have been examined with a microreactor-GC NO+CO reaction system and the catalysts characterized by BET, TPR, TG-DTA, XRD and NO-TPD. Experimental results show that the CuO/Ti0.5Zr0.5O2 activities increase with increase in CuO loading.

1846

Synthesis, structure and electrochemical properties of ruthenium complexes with some tridentate O,N,O-donor ligands

 

 

 

 

 

 

 

Prasanta Kumar Sinha, Larry R Falvello & Samaresh Bhattacharya*

 

 

1853

Synthesis, characterization and reactions of metal complexes of 2-(1-formyl-ferrocene) thiazoline and 2-methyl-2-(1-ferrocene)thiazoline

 

 

 

Kamalendu Dey*, Sanjib Mukhopadhyay & Saikat Sarkar

 

1863

Cadmium complexes stabilized by bis-benzimi-dazlolyl derivatives

 

 

 

 

 

 

 

 

Shivakumaraiah & N M Nanje Gowda*

 

Cadmium halides/perchlorate react with bis-benzimidazolyl ligands 1,3-bis(benzimidazol-2-yl) benzene (L1), 1,3-bis(1-methylbenzimidazol-2-yl) benzene (L2) and 2,6-bis(1-methylbenzimidazol-2-yl) pyridine (L3) in ethanol to produce complexes of the compositions CdX2L1.nH2O (X = Cl, n = 1, X = Br or I, n = 2), (CdCl2)2L2, CdX2L (X = Br or I, L = L2; X = Cl, Br or I, L = L3), Cd2(L1)3(ClO4)4.6H2O and Cd(L)2(ClO4)2.nH2O (L = L2, n = 2; L = L3, n = 0).

Notes

1868

A study on partial molar volumes of some organic acids in binary aqueous solutions of urea at different temperatures

 

 

 

M L Parmar*, O P Sharma & M K Guleria

 

Partial molar volumes of ascorbic, citric and tartaric acids, at different concentrations have been determined in binary aqueous solutions of urea. The data have been evaluated using Masson equation and the obtained parameters have been interpreted in terms of solute-solute and solute-solvent interactions. All the three organic acids behave as structure breakers.

1872

Densities and partial molal volumes of sodium tetrafluoroborate aqueous solutions at 20°C

 

 

 

 

William J Crooks III* & Jerry D Christian

 

Densities of solutions of NaBF4 in H2O have been determined at 20.00 °C over the concentration range 0.05 to 9.0 molal (0 to 50 wt%) NaBF4. The results are represented by d (g/mL, 20°C) = 9.726´10-5 m3 - 3.2157 x10-3 m2 + 6.7447´10-2 m + 0.99843, where d is density and m is molality. This equation has been used to derive concentrative properties for NaBF4 solutions.

1876

Excess volume and viscosity of ethoxy ethanol with n-butylamine, sec-butylamine, tert-butylamine, n-hexylamine, n-octylamine and cyclohexylamine

 

 

M C S. Subha*, G Narayana Swamy, M Eswari Bai & K S V Krishna Rao

 

Densities and viscosities of ethoxy ethanol with n-butyl-amine, sec-butylamine, tert-butylamine, n-hexylamine, n-octylamine and cyclohexylamine have been measured at 308.15 K. From the experimental data the excess volume, deviation in viscosity and the excess molar Gibb’s free energy for the activation of viscous flow have been computed.

1882

Kinetic and mechanistic approach of the inter-action of glycylglycine with cis-[Pt(en)(H2O)2] (ClO4)2  and cis-[Pt(dmen) (H2O)2](ClO4)2 (en = ethylenediamine, dmen = N,N¢-dimethylethylene-diamine) in aqueous medium

  

 

Sujit K Bera & Gauri S De*

 

The kinetics of the interaction of glycylglycine with cis-[Pt(en)(H2O)2](ClO4)2 and cis-[Pt(dmen)(H2O)2] (ClO4)2 (en = ethylenediamine, dmen = N,N¢-dimethyl-ethylenediamine) have been studied spectrophoto-metrically as a function of [substrate complex], [glycylglycine] and temperature at pH 4.0. The low enthalpy of activation and large negative values of entropy of activation indicate an associative mode of activation.

1887

 Kinetics and mechanism of oxidation of ascorbic acid by molybdenum(VI) in acidic medium

 

  

 

P P Tripathi & R M Mehrotra*

 

 The kinetics of oxidation of ascorbic acid (H2A) by molybdenum (VI) has been investigated in acidic medium by absorbance measurement. The value of energy of activation, enthalpy of activation and entropy of activation have been computed as 63.8 kJ mol-1, 61.3 kJ mol-1 and –57.51 JK-1 mol-1, respectively.

1890

Kinetics and mechanism of reduction of ferricytochrome C by vanadate in phosphate buffers

 

 

 

 

N R Suja, N Sridevi & K K Mohammed Yusuff*

 

The kinetics and mechanism of the reaction between ferricytochrome C and vanadate has been investigated spectrophotometrically employing [vanadate] >> [ferricytochrome C]. The deprotonation constant for ferricytochrome C and the second order rate constant for the present reaction at 30°C have been determined from this study as (1.01 ± 0.05) ´ 10-7 mol dm-3 and 95.2. ± 0.5 dm3 mol-1 s-1 respectively.

1892

Synthesis, characterization, electrical and biological studies of Cr(III), Mn(III), Fe(III), Ti(III), VO(IV), Th(IV), Zr(IV) and UO2(VI) polychelates with bis-bidentate Schiff base

 

 

A S Aswar*, A D Bansod, S R Aswale & P R Mandlik

 

 

1897

Synthesis and characterization of mixed ligand complexes of Co(II) and Fe(III) ions with malonic acid and heterocyclic amines

 

 

 

 

 

M Saidul Islam*, Md. Belayet Hossain & Md. Yeamin Reza

 

1901

Synthesis, structure and properties of [Cu(L)(NCO)]X (L = tetradentate schiff bases; X = ClO4, PF6)

 

 

 

 

 

Sk. Hafijur Rahaman, Rajarshi Ghosh, Doyel Bose, Hoong-Kun Fun & Barindra Kumar Ghosh*

 

 

1906

Synthesis and spectroscopic investigations of oxovanadium(IV) derivatives with 1,1¢-diacetyl-ferrocenyl-bis(hydrazones)

 

 

 

Jitendra Kumar Pandey, Om Prakash Pandey & Soumitra Kumar Sengupta*

 

1911

Synthesis and characterization of  2,2¢-bipyridine adducts of bis (N,N-dialkylcarbodithioato-S,S¢) Zn(II) and crystal structure of (2,2¢bipyridine)bis (N,N-diethylcarbodithioato-S,S¢) Zn(II) and (2,2¢bipyridine)bis(pyrrolinecarbo dithioato-S,S¢) Zn(II)

 

 

 

 

Handong Yin*, Chuanhua Wang & Qiuju Xing

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1815-1823

 

A quantum mechanical localized molecular orbital study of the physical process of the planar (D3h) to pyramidal (C3v) structural reorganization of trifluoro methyl cation

Dulal C Ghosh* & Arindam Chakraborty

 

An important carbocation, CF3+ occurs in planar (D3h) structure but quickly reorganizes to pyramidal (C3v) form in chemical response prior to the event of chemical reaction. The structural reorganization process is associated with a significant stretching of C–F bond and redistribution of charge density. A quantum mechanical study of the physical process of structural evolution of CF3+ system is carried out invoking the localization technique of Sinanoğlu and energy partitioning analysis of Kollmar and Fischer. Quantum mechanical hybridizations in the molecule, and the energy of the ‘C–F’ bond are evaluated in a number of generated conformations of the chemical species. A number of diverse parameters that can correlate the energetic, kinetic and structural aspects of the ionic species are also evaluated as a function of structural deformation. The computed quantities are found to be important inputs in explaining the energetic and binding aspects of the evolution of molecular shape, and in correlating the chemical reactivity of the CF3+ system. A rationale of the pattern of charge rearrangement in the ionic species is put forward in terms of the dynamic variation of electronegativity with the evolution of conformations. Results demonstrate that the variation of the strength of the C–F bond and the percentage of s-character of the hybrids of ‘C’ and ‘F’ atoms forming the bond as a function of D3h to C3v structural evolution are in accordance with suggestions of Brown and Coulson in this regard.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1824-1831

 

Semi-empirical calculation of the transport properties of the CH4-noble gas mixtures from the interaction potential energy function using the inversion method

Behzad Haghighi*, Mohammad Fathabadi & Mohammad Mehdi Papari

 

Viscosity, diffusion coefficients, and thermal diffusion factors for five equimolar binary gas mixtures of CH4-noble gases have been determined from the principle of corresponding states of viscosity by the inversion technique. The Lennard-Jones 12-6 potential energy function is used as the initial model potential required by the technique. The interaction potential energies from the inversion procedure reproduce viscosities within 1%, diffusion coefficients within 5%, and thermal diffusion factors within 25%.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1832-1837

 

Triplet state characteristics of IR laser dyes: A pulse radiolysis study

M Rele, A K Singh, D K Palit & T Mukherjee*

 

The IR-dyes, having the absorption maximum in the range of 600 nm to 1100 nm, are expected to have very low triplet energy level. The triplet-triplet (T-T) absorption spectra and decay characteristics have been investigated for four IR laser dyes, namely, IR-140, IR-144, Q-Switch 1 and Q-Switch 5. Triplet state of these IR dyes are generated by electron pulse radiolysis in benzene-benzonitrile (BZ-BZN 80:20, % v/v) solvent mixture. Energy transfer from the pulse radiolytically generated anthracene triplet confirms the formation of triplet state of these IR dyes. Triplet state characteristics of these IR dyes have been measured. Using various triplet donors and acceptors, the triplet energy levels of these dyes have been estimated.

 

IPC Code: Int Cl7. G01N 21/00; G01J 3/00; C09B

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1838-1845

 

Studies of Ti0.5Zr0.5O2 supported CuO catalysts for NO + CO reaction

Guang-hui Ding, Xiao-yuan Jiang*, Yue-juan Wang & Xiao-ming Zheng

 

The activities of CuO supported on Ti0.5Zr0.5O2 have been examined with a  microreactor-GC NO+CO reaction system and the catalysts characterized by BET, TPR,TG-DTA, XRD and NO-TPD. Experimental results show that the CuO/Ti0.5Zr0.5O2 activities increase with increase in CuO loading. To obtain 99% NO conversion, the reaction temperature needed to be 350°C in air but only 200°C in H2 atmosphere. TPR analysis shows two peaks (α and β peaks) at CuO loading of 12%, while a third peak (γ peak) occurs with higher CuO loading at 300°C. The α peak is attributed to highly dispersed CuO, the β peak to isolated CuO and the γ peak to crystal CuO. TG-DTA also shows endothermic peak at low temperature (120°C) and exothermic peak at high temperature (725°C), indicating the completion of ZrTiO4 crystallization. From the XRD analysis, it has been found that there is no CuO crystal diffraction peaks at 12% CuO loading, but two CuO crystal diffraction peaks at 2θ 35.5° and 38.7° are present at 18% CuO loading. With increase in CuO loading, the intensity of CuO diffraction peaks is increased. In addition, NO-TPD analysis shows that NO adsorption and desorption by Ti0.5Zr0.5O2 in air are similar to those in H2 atmosphere. In air atmosphere, both CuO/Ti0.5Zr0.5O2 and Ti0.5Zr0.5O2 have two adsorption peaks, but the former has lower desorption peak temperature than the latter, suggesting that the activity of NO decomposition by CuO/Ti0.5Zr0.5O2 is higher than that by Ti0.5Zr0.5O2. In H2 atmosphere, the high temperature desorption peak disappears and there only exists one low temperature desorption peak at 150°C, inferring that the high temperature adsorption site is probably Cu2+ and the low temperature adsorption site is Cu0.

 

IPC Code: Int. Cl.7  B01J  21/06

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1846-1852

 

Synthesis, structure and electrochemical properties of ruthenium complexes
with some tridentate O,N,O-donor ligands

Prasanta Kumar Sinhaa, Larry R Falvellob & Samaresh Bhattacharyaa*

 

Reaction of four phenolate ligands, viz. N-(2-hydroxyphenyl)salicylaldimine (H2L1), 2,2¢-dihydroxyazobenzene (H2L2), N-(2-carboxyphenyl)salicylaldimine (H2L3) and 2-carboxy-2¢-hydroxy-5¢-methylazobenzene (H2L4) (abbreviated in general as H2L, where H stands for the acidic protons), has been carried out with [Ru(trpy)Cl3] (trpy = 2,2¢,2²-terpyridine). The H2L1 and H2L2 ligands form complexes of the type [Ru(trpy)(L)]. Reaction with H2L3 does not afford any ruthenium complex. The H2L4 ligand forms a complex of different type, viz., [Ru(trpy)(HL4)(CH3CN)]+, isolated as the perchlorate salt. Structure of the [Ru(trpy)(HL4)(CH3CN)]ClO4 complex has been determined by X-ray crystallography. The HL4 ligand is bound to ruthenium as a bidentate N,O-donor and the carboxylate oxygen does not participate in coordination. All the three complexes are diamagnetic (low-spin d6, S=0) and show intense MLCT transitions in the visible region. Cyclic voltammetric studies on these complexes show Ru(II)-Ru(III) oxidation within 0.00-0.19 V vs SCE and a Ru(III)-Ru(IV) oxidation within 1.08-1.48 V vs SCE. A one-electron reduction of the coordinated trpy ligand is also observed in all the complexes near –1.4 V vs SCE.

 

IPC Code: Int. Cl.7 C07F 15/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1853-1862

 

Synthesis, characterization and reactions of metal complexes of 2-(1-formyl-ferrocene)thiazoline and 2-methyl-2-(1-ferrocene)thiazoline

Kamalendu Dey*, Sanjib Mukhopadhyay & Saikat Sarkar

 

Reaction of 1-formylferrocene and 1-acetylferrocene with 2-aminoethanethiol yielded 2-(1-formylferrocene)thiazoline (Ffthz) and 2-methyl-2-(1-ferrocene)thiazoline (Mfthz) rather than the corresponding schiff bases 2-(1-formyl­ferrocene)­iminoethanethiol (HFfimethol) and 2-Methyl-2-(1-ferrocene)iminoethanethiol (HMfimethol), respectively. The reaction of Ffthz and Mfthz with M(OAc)2.nH2O (M = Co, Ni, Cu, Zn, Cd), MCl2. nH2O (M = Cu, Co, Ni), M(NO3)2. nH2O (M = Cu, Co, Ni), Me2SnCl2, MeSnCl3, (p-C5H5)2MCl2 (M = Ti, Zr), (p-C5H5)TiCl3, (p-C5H5)TiCl2(OMe) and TiCl2(OMe)2, under varied reaction conditions afforded the corresponding schiff base complexes of the metal ions. Monoanion of the schiff base (Ffimethol)1– or (Mfimethol)1– functions as bidentate NS donor ligand in the complexes. Reactions of [MeSn(Ffimethol)2Cl] and [(p-C5H5)Ti(Ffimethol)2Cl], isolated in this study, with MeSH, Me2NSiMe3, Me3Si(N3) and Me3SiCºC-Ph have also been studied leading to the synthesis of many new organotin(IV) and organotitanium(IV) compounds. The compounds have been characterised on the basis of elemental analyses, molar conductances, molecular weights, magnetic susceptibilities and spectroscopic (IR, 1H NMR, UV-vis) data.

 

IPC Code: Int Cl7. C07F 1/08; C07F 3/06; C07F 3/08; C07F 7/22; C07F 15/04; C07F 15/06

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1863-1867

 

Cadmium complexes stabilized by bis-benzimidazolyl derivatives

Shivakumaraiah & N M Nanje Gowda*

 

Cadmium halides/perchlorate react with bis-benzimidazolyl ligands (1) 1,3-bis(benzimidazol-2-yl)benzene (L1), 1,3-bis(1-methylbenzimidazol-2-yl)benzene (L2) and 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (L3) in ethanol to produce complexes of the compositions CdX2L1.nH2O (X = Cl, n = 1, X = Br or I, n = 2), (CdCl2)2L2, CdX2L (X = Br or I, L = L2; X = Cl, Br or I, L = L3), Cd2(L1)3(ClO4)4.6H2O and Cd(L)2(ClO4)2.nH2O (L = L2, n = 2; L = L3, n = 0). The complexes have been characterized by elemental analyses, conductance measurements, IR, 1H and 13C NMR spectral studies as well as thermal analysis.

 

IPC Code: Int. Cl7. C07F 3/08

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1868-1871

 

A study on partial molar volumes of some organic acids in binary aqueous solutions of urea
at different temperatures

M L Parmar*, O P Sharma & M K Guleria

 

Partial molar  volumes  of  ascorbic, citric  and tartaric acids, at different concentrations have been determined in binary  aqueou s solutions of urea (1, 2, 3, 5 and7 m of urea) at 298 K and in 1. m urea at four  equidistant temperatures. The data have been evaluated using Masson equation and the obtained parameters have been interpreted in terms of solute-solute and solute-solvent interactions. The partial molar volumes vary with temperature as a power series of temperature. Structure making/breaking capacities of the organic acids have been inferred from the sign of [2fvo/T2]p, i.e. second derivative of partial molar volume with respect to temperature at constant pressure. All the three organic acids behave as structure breakers in binary aqueous solutions of urea.

 

IPC Code: Int. Cl.7 G01N 9/04

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1872-1875

 

Densities and partial molal volumes of sodium tetrafluoroborate aqueous solutions at 20°C

 

William J Crooks III* & Jerry D Christian

 

Densities of solutions of NaBF4 in H2O have been determined at 20.00 °C over the concentration range 0.05 to 9.0 molal (0 to 50 wt%) NaBF4. The results are represented by d (g/mL, 20°C) = 9.726´10-5 m3 - 3.2157´10-3 m2 + 6.7447´10-2 m + 0.99843, where d is density and m is molality. This equation has been used to derive concentrative properties for NaBF4 solutions. The raw density data have been used to derive partial molal volumes. The partial molal volume at infinite dilution is 37.6 ± 2.7 mL/mol at 20°C. The partial molal volume at 20°C is represented by v2 = 37.5 + 9.22m1/2 – 2.92m from 0 to 2.5 m NaBF4 and v2 = 44.6 + 0.081m from 2.5 to 9 m NaBF4.

 

IPC Code: Int Cl.7 G01N 9/04

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1876-1881

 

Excess volume and viscosity of ethoxy ethanol with n-butylamine, sec-butylamine,
tert-butylamine, n-hexylamine, n-octylamine and cyclohexylamine

M C S Subha*, G Narayana Swamy, M Eswari Bai & K S V Krishna Rao

 

Densities and viscosities of ethoxy ethanol (EEL) with n-butylamine (NBA), sec-butylamine (SBA), tert-butylamine (TBA), n-hexylamine (NHA), n-octylamine (NOA) and cyclohexylamine (CHA) have been measured at 308.15 K. From the experimental data the excess volume (VE), deviation in viscosity ( hE) and the excess molar Gibb’s free energy of the activation of viscous flow (G*E) have been computed and presented as function of composition. The parameter d1 of the Grunberg and Nissan has been calculated. The observed variations of the properties for the above mixtures conclude that the interactions between unlike molecules predominate over the dissociation effects in the individual components. It is also evident that the presence of strong interactions between unlike molecules is predominant and characterized by the negative VE and positive  hE, G*E and d1 values. The excess volume, deviation in viscosity and excess molar Gibb’s free energy of the activation of viscous flow have been fitted to Redlich-Kister equation to derive the coefficients and standard deviations.

 

IPC Code: Int Cl7. G01N 9/04; G01N 11/02

 

 

 

Indian Journal of Chemistry

Vol. 43A, September 2004, pp. 1882-1886

 

Kinetic and mechanistic approach of the interaction of glycylglycine with cis-[Pt(en)(H2O)2](ClO4)2 and cis [Pt(dmen)(H2O)2](ClO4)2 (en = ethylenediamine, dmen = N,N¢-dimethylethylenediamine) in aqueous medium

Sujit K Bera & Gauri S De*

 

The kinetics of the interaction of glycylglycine (diglycine) with cis-[Pt(en)(H2O)2](ClO4)2 and cis-[Pt(dmen)(H2O)2](ClO4)2 (en = ethylenediamine, dmen = N,N¢-dimethylethylenediamine) have been studied spectrophotometrically as a function of [substrate complex], [glycylglycine] and temperature at a particular pH (4.0) where the substrate complex exists predominantly as the diaqua species and glycylglycine (diglycine) as the zwitterion. The reaction has been found to proceed through two consecutive steps. The first step involves the ligand assisted anation, while the second step involves chelation when the second aqua ligand is displaced. Rate constants have been evaluated using Weyh and Hamm method. Activation parameters for both the steps have also been calculated using Eyring equation. The low enthalpy of activation and large negative values of entropy of activation indicate an associative mode of activation for both steps.

 

 

 

Indian Journal of Chemistry

Vol. 43A, September 2004, pp. 1887-1889

 

Kinetics and mechanism of oxidation of ascorbic acid by molybdenum(VI) in acidic medium

P P Tripathi & R M Mehrotra*

 

The kinetics of oxidation of ascorbic acid (H2A) by molybdenum (VI) has been investigated in acidic medium by absorbance measurement. The reaction shows a first order dependence in both ascorbic acid and Mo(VI). The order in hydrogen ion has been found to be inverse first order. The reaction rate increases with increase in ionic strength. The value of energy of activation, enthalpy of activation and entropy of activation have been computed as 63.8 kJ mol-1, 61.3 kJ mol-1 and –57.51 JK-1 mol-1 respectively. A mechanism consistent with the experimental data has also been suggested.

 

IPC Code: Int.Cl.7 C07B 35/04

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1890-1891

 

Kinetics and mechanism of reduction of ferricytochrome C by vanadate in phosphate buffers

N R Suja, N Sridevi & K K Mohammed Yusuff*

 

The kinetics and mechanism of the reaction between ferricytochrome C and vanadate has been investigated spectrophotometrically employing [vanadate] >> [ferricytochrome C]. The reaction exhibits first order each in [ferricytochrome C] and [vanadate ion]. The pseudo-first order rate constant decreases with an increase in ionic strength and increases with an increase in pH in the range 7 to 8. A suitable mechanism has been proposed on the basis of these results. The deprotonation constant for ferricytochrome C and the second order rate constant for the present reaction at 30°C have been determined from this study  as (1.01±0.05)´10-7 mol dm-3 and 95.2±0.5 dm3 mol-1 s-1 respectively.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1892-1896

 

Synthesis, characterization, electrical and biological studies of Cr(III), Mn(III), Fe(III), Ti(III), VO(IV), Th(IV), Zr(IV) and UO2(VI) polychelates with bis-bidentate Schiff base

A S Aswar*, A D Bansod, S R Aswale & P R Mandlik

 

The polychelates of Cr(III), Mn(III), Fe(III), Ti(III), VO(IV), Th(IV), Zr(IV) and UO2 (VI) with bis-bidentate Schiff base derived from 4,4¢-bis[salicylaldehyde-5)-azo] diphenyl methane and aniline have been synthesized. The resulting compounds have been characterized on the basis of elemental analyses, reflectance and infrared spectral studies, magnetic measurements and thermogravimetric analysis and are found to have the general formula [M(BPSADM) xH2O]n. The ligand (H2BPSADM) act as a bis-bidentate molecule coordinating through the phenolic oxygen and azomethine nitrogen atoms. The thermal data have been analyzed for the kinetic parameters by using Broido’s method. The thermal stability of these chelates decreases in the order Zr>Mn>Th>UO2>Cr>Ti>Fe>VO. The thermal activation energy lies in the range 38.68 to 55.18 kj mol-l and the decomposition follows first order kinetics. The solid state conductivity of the ligand and its polychelates have been studied over the temperature range 313-493 K and the chelates are found to show semiconducting behaviour. The activation energy of the electrical conduction lies in the range 0.912 to 0.315 eV. The ligand and its polychelates have also been screened for their antimicrobial activities using various microorganisms and all of them have been found to be moderately active against the organisms.

 

IPC Code: Int. Cl.7 C07F 15/02; C07F 11/00; C07F 13/00; C07F 7/28; C07F 9/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1897-1900

 

Synthesis and characterization of mixed ligand complexes of Co(II) and Fe(III) ions with malonic acid and heterocyclic amines

M Saidul Islam*, Md. Belayet Hossain & Md. Yeamin Reza

 

The preparation and characterization of mixed ligand complexes of Co(II) and Fe(III) ions with malonic acid and heterocyclic amines are described here. The general formula of the complexes are; [M(MO)L] and K[M(MO)L], [where, M=Co(II) (1-6), Fe(II) (7-8); MO=C3H2O4 (1-6), 2C3H2O4 (7-8); L=C6H5N (1), C5H6N2 (2), 2C9H7N (3,4,7,8), C6H6NO (5), C9H6NO (6)]. IR spectra of the complexes confirm the coordination of metal ion with ligands. The magnetic measurements indicate that the Co(II) complexes (1-6) are paramagnetic, having magnetic moment 3.91-4.21 B.M. The Co(II) complexes are assumed to have tetrahedral and the Fe(III) complexes have octahedral structure based on the electronic spectra and magnetic measurements.

 

IPC Code: Int. Cl.7 C07F 15/02; C07F 15/06

 

 

 

Indian Journal of Chemistry

Vol. 43A, September 2004, pp. 1901-1905

 

Synthesis, structure and properties of [Cu(L)(NCO)]X (L = tetradentate schiff bases; X = ClO4, PF6)

Sk. Hafijur Rahaman, Rajarshi Ghosh, Doyel Bose, Hoong-Kun Fun &

Barindra Kumar Ghosh*

 

Four copper(II) complexes of the  type [Cu(L)(NCO)]X (1-4) [L=N,N¢-(bis(pyridin-2-yl)formylidene)butane-1,4-diamine (bpfd) or N,N¢-(bis(pyridin-2-yl)benzylidene)butane-1,4-diamine (bpbd); X = ClO4, PF6] have been synthesised and characterised on the basis of microanalytical, spectroscopic, magnetic, electrochemical and other physicochemical properties. X-ray diffraction study of complex 1 (L = bpfd, X = ClO4) reveals copper(II) ion in a distorted trigonal bipyramidal environment through coordination of the metal centre by two pyridine N atoms and two imine N atoms of the schiff base with the fifth  position occupied with N atom of terminal NCO-. The tetradentate chelator is folded in the butylenic part. IR spectra of the complexes show asymmetric and symmetric stretching nNCO vibrations at ~2250 and ~1320 cm-1 respectively indicating N-bonding of NCO-. Electrochemical electron transfer study reveals CuII-CuI reduction in methanolic solutions.

 

IPC Code: Int. Cl.7 C07F 1/08; C07F 9/14

 

 

 

Indian Journal of Chemistry Vol. 43A, September 2004, pp. 1906-1910

 

Synthesis and spectroscopic investigations of oxovanadium(IV) derivatives with 1,
1¢-diacetylferrocenyl-bis(hydrazones)

Jitendra Kumar Pandey, Om Prakash Pandey & Soumitra Kumar Sengupta*

 

The reactions of oxovanadium(IV) sulphate with bis(hydrazones) (LH2) derived from 1,1¢-diacetylferrocene and different aromatic acid/pyridine carboxylic acid hydrazides, in ethanol gives the complexes of type [VO(L)]. Tentative structural conclusions are drawn for the complexes based upon analyses, conductance, magnetic moments and spectral (IR, electronic and EPR) data.

 

IPC Code: Int. Cl7  C08 59/70

 

 

 

Indian Journal of Chemistry

 Vol. 43A, September 2004, pp. 1911-1914

 

Synthesis and characterization of 2,2¢-bipyridine adducts of bis(N,N-dialkylcarbodithioato-S,S¢)Zn(II) and crystal structure of (2,2¢-bipyridine)bis
(N,N-diethylcarbodithioato-S,S¢)Zn(II) and
(2,2¢-bipyridine)bis(pyrrolinecarbo-dithioato-S,S¢)Zn(II)

Handong Yin*, Chuanhua Wang & Qiuju Xing

 

Seven novel 2,2¢-bipyridine adducts of bis(N,N-dialkylcarbo dithioato-S,S’)Zn(II) have been synthesized and characterized by elemental analysis and IR. The crystal and molecule structures of (2,2¢-bipyridine)bis(N,N-diethylcarbodithioato-S,S¢) Zn(II) 1 and (2,2¢-bipyridine)bis(pyrrolinecarbodithioato-S,S¢) Zn(II) 3 have been determined by X-ray single crystal diffraction. In complexes 1 and 3, the structures consist of discrete molecules containing six-coordinate Zn atom in a distorted octahedral configuration.

 

IPC Code: Int. Cl7. C07F 3/06