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Indian Journal of Chemistry

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

 

 

 

VOLUME 43A

NUMBER 5

MAY 2004

 

 

CONTENTS

 

 

Papers

 1033

 

 Microkinetic model studies of alloying effects on the CO+NO+O2 reactions over Pt-Rh nanocatalysts

 

 

 

Abir De Sarkar* & Badal C Khanra

 

 

 Microkinetic model has been used to study the kinetics of CO+NO+O2 reactions on Pt-Rh nanocatalysts. The alloy particles show an intermediate behavior for the CO+O2 reaction. For the CO+NO reaction, the kinetic behavior of alloy particles are close to that of Rh, while for the CO+NO+O2 reaction, it is very close to that of Pt. The rates of CO+O2 and CO+NO+O2 reactions are higher than that of CO+NO reaction on Pt, Rh and Pt-Rh nanocatalysts.

 1039

 Synthesis, characterization and catalytic properties of SAPO-11, -31 and 41 molecular sieves

 

N Venkatathri* & R Srivastava

 

 Medium pore molecular sieves, SAPO-11, SAPO-31 and SAPO-41, have been synthesized and characterized. Catalytic activities of these materials in the esterification of phathlic anhydride with different alcohols is in the order: SAPO-41> SAPO-11> SAPO-31.

 1044

 Electrochemical oxidation of 6-thioxanthine at pyrolytic graphite electrode

 

 

Rajendra N Goyal*, Udai P Singh & Adil A Abdullah

 

 Electrochemical oxidation of 6-thioxanthine has been studied in phosphate buffers of pH 1.2-11.0 using linear and cyclic sweep voltammetry, coulometry, controlled potential electrolysis and spectral studies. The studies show that in acidic medium, thio group of 6-thioxanthine exists as S-H, whereas in neutral and basic medium, thio group is in the form of C=S.

1051

 Kinetics of reactions of o-(2,4-dinitrophenyl) indanone oxime with cyclohexylamine, piperidine and ethanolamine in acetonitrile

 

 

Gurudas Bhattacharjee*, Ashok Kumar Singh, Rupam Singh & Priti Gairola

 

 Effect of nucleophile on the reaction of o-(2,4-dinitrophenyl) indanone oxime (DNPIO) has been studied with cyclohexylamine (CHA), ethanolamine (ETA) and piperidine (PIP) in acetonitrile at 35 0.1oC. Reactions of DNPIO with CHA and ETA are kinetically of second order while the reactions with PIP are wholly base catalyzed and have a third order dependence on PIP.

 1056

 Kinetics and mechanism of the oxidative regeneration of carbonyl compounds from oximes by [bis(trifluoroacetoxy)iodo]benzene

 

 Alpna Kansara, Pradeep K Sharma & Kalyan K Banerji*

 

 The oxidation of several aldo- and keto-oximes by [bis(trifluoroacetoxy)iodo] benzene (TFAIB), in aqueous acetic acid exhibits first order dependence on both the oxime and TFIAB. The oxidation of ketoximes is slower than that of aldoximes. The oxidation of aliphatic oximes correlates well in terms of Pavelich-Taft dual substituent-parameter equation.

Text Box: CrIII

 

Text Box: CrIV

 

Text Box: CrVI

 

 

1060

 A kinetic study of the reduction of chromium(VI) by thiourea in the absence and presence of manganese(II), cerium(IV) and ethylenediamine-tetra aceticacid (EDTA)

 

 

  

Zaheer Khan*, Mohammad Yousuf Dar, Prabijna S S Babu & Kabir-ud-Din

 

 

 The kinetics of reduction of Cr(VI) by thiourea has been studied spectrophotometrically in an HClO4 medium. The reaction follows overall third order kinetics, first order each in Cr(VI), thiourea and HClO4. The spectrophotometric study indicates that the reduction of chromium(VI) follows the sequence


where, R= thiourea.

 

 

1066

 

More insight into the crystal structure of [Co(H2O)4(4-nba)2]2H2O (4-nba=para-nitro-benzoate): An unprecedented hydrogen bonded supramolecular network

 

  

B R Srinivasan*, Sarvesh C Sawant & Samar K Das

 

 

 1076

 Iron(II) reduction, protonation and iron(III) equilibria of some chlorocobalt(III)dioxime complexes

 

 

 

 

A Dayalan* & A Xavier

 

 

 Cobalt(III) complexes of the type [Co(dpgH)2- (s-py)Cl],where dpgH=diphenylethanedione dioximate, s-py= pyridine (py) or a substituted pyridine like nicotinic acid, quinoline or 8-hydroxy quinoline, have been prepared and their iron(II) reductions have been studied at 300 nm. An inverse acid dependence on the rate of reduction of the complexes indicates the oxime bridged inner-sphere reduction with equilibria involving H+.

Notes

 1083

Diamino-functionalized mesoporous molecular sieve anchoring V(IV) and Mo(VI) complexes as catalyst for alkene epoxidation

 

Hengquan Yang, Gaoyong Zhang*, Xinlin Hong & Yinyan Zhu

 

 

 

 

 1088

 Spectroscopic and surface studies of catalytically active Zn1-xMnxFe2O4 (X= 0, 0.25, 0.50, 0.75 and 1) ferrospinel systems

 

A Radheshyam, Reena Dwivedi, Vanga S Reddy, R Prasad*, Tushar Banerjee & Pankaj Patidar

 

 

 Zn-Mn ferrospinel systems have been characterized by ESR, X-ray diffraction, FTIR, BET surface area and ammonia desorption methods. It has been observed that ESR spectra of systems possessing high x values are highly magnetic in nature. Distortion of the system is also observed with increasing Mn content in the samples.

 1092

 

 Solvation models in the reaction between benzyl bromide and diphenyl amine

 

 

S Ranga Reddy & P Manikyamba*

 

 

 The effect of different protic and dipolar aprotic solvents on the rate of the reaction between benzyl bromide and diphenyl amine has been studied. Correlation of the rate constants with different solvent parameters indicates that the polarity, nucleophilicity and hydrogen bond donor ability of the solvent simultaneously influence the rate.

1095

 Determination of amino acids separated by micellar electrokinetic chromatography after pre-column derivatization with o-phthalaldehyde

 

 A Durgbanshi, S Sharma, M Shelke, D Bose, A Asthana & S K Sanghi*

 

 

 A simple, sensitive and rapid analytical method has been developed for the determination of amino acids separated by micellar electrokinetic chromatography after pre-column derivatization with o-phthalaldehyde. The separated amino acids have been detected using ultraviolet as well as electrochemical detection modes.

 1099

 

 Study of the interaction of butyl rodamine B with DNA and the determination of DNA based on resonance light scattering measurements

 

  

Gong-wu Song*, Zhao-xia Cai & Ling Li

 

 

 A new method for determination of nucleic acids in aqueous solutions has been developed, based on the enhancement of resonance light scattering (RLS) of butyl rhodamine B (BRB) by nucleic acids under acidic condition at 400 nm. The intensity of resonance light scattering is found to be proportional to the DNA concentration. Under the experimental conditions, there is little interference from proteins, nucleosides and most metal ions.

 1102

 

 Crystallographic and spectroscopic studies of luminescent copper(I) complex [(PPh3)2Cu(S2COMe)]-Insertion reaction of carbon disulfide

 

   

Zhao Dong*, Li Guanliang, Zhao Liang , Zhang Chuanjian & Sun Yuan

 

 

 

 1106

 Spectral and thermal characterization of new biomimetic polydentate amide ligands

 

  

 

Bhagwan S Garg*, Meenu Sarbhai & Deo Nandan Kumar

 

 

 

 1109

 Synthesis and crystal structure of triphenyltin diphenylthiocarbazone

 

 

 

 

 

 

Rufen Zhang, Feng Li & Chunlin Ma*

 

 

 1112

 Synthesis, characterisation and redox behaviour of mixed ligand complexes of osmium(II/III/IV)-phosphines

 

 

Habibar Chowdhury, Jaya Banerjee, Sk Hafijur Rahaman, Doyel Bose &Barindra Kumar Ghosh*

 

 

1119

 

 Synthesis, characterisation and X-ray structure of a mononuclear zinc(II)azido complex containing tetradentate schiff base

 

 

 

 

Jaya Banerjee, Doyel Bose, Sk Hafijur Rahaman, Rosa D Bailey Walsh, M J Zaworotko & Barindra K Ghosh*

 

 

 

 1123

 

Synthesis and characterization of some 6,7 and 8-coordinate monomeric complexes of tungsten obtained from reaction of [W(CO)3(MeCN)3] with pyridine-2-thiol (pySH) and PPh3

 

 

Anjumanara, Noorjahan Begum, Farzana K Camellia, Shariff E Kabir* & Kalipada Kundu*

 

 

 1126

Polymeric and binuclear monomeric Mn(II) chelates of some multidentate azo compounds derived from b-diketones

 

  

 

K Y El-Baradie*, R M Issa & M Gaber

 

 1131

 Synthesis and anti-HIV activity of metal complexes of SRR-SB3

 

 

  

 

Minu G Bhowon* & B S Jhaumeer Laulloo

 

 

 1134

Synthesis and characterization of dioxarsolanes and -arsenanes complexes using O,O-alkylene dithiophosphate

 

  

Romesh Chander, B L Kalsotra & Sushil K Pandey*

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

 Vol. 43A, May 2004, pp. 1033-1038

 

Microkinetic model studies of alloying effects on the CO+NO+O2 reactions over Pt-Rh nanocatalysts

Abir De Sarkar* & Badal C Khanra

 

Microkinetic model has been used to study the kinetics of CO+NO+O2 reactions on Pt-Rh nanocatalysts. The alloy particles show an intermediate behavior for the CO+O2 reaction. For the CO+NO reaction, the kinetic behavior of alloy particles are close to that of Rh, while for the CO+NO+O2 reaction, it is very close to that of Pt. The rate of CO+O2 and CO+NO+O2 reactions is higher than that of CO+NO reaction on Pt, Rh and Pt-Rh nanocatalysts. The light-off temperature in case of CO+NO reaction is delayed in the absence of oxygen. The overall kinetics of the CO+NO+O2 reaction on Rh is dominated by CO+NO reaction kinetics rather than by CO+O2 reaction kinetics which has a higher inherent rate. The scenario reverses itself on Pt nanoparticles. The magnitude of the NO inhibition effect on the CO oxidation by O2 is considerably smaller on Pt than on Rh. The simulated results are in qualitative agreement with the experimental findings.

PACS : 68.43.Mn ; 82.20.Pm ; 82.65.+r ; 82.45.Jn ; 82.20.Wt

IPC Code: Int. Cl.7  B01J  23/42,  B01J  23/36

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1039-1043

 

Synthesis, characterization and catalytic properties of SAPO-11, -31 and 41 molecular sieves

N Venkatathri* & R Srivastava

 

Medium pore molecular sieves, SAPO-11, SAPO-31 and SAPO-41, have been synthesized using di-n-propylamine and diethylamine as the organic template. They have been characterized by various methods such as elemental analysis, X-ray powder diffraction, solid state MAS NMR spectroscopy, and FT-IR spectroscopy in the framework and hydroxyl regions. Catalytic activities of these materials in the esterification of phthalic anhydride with different alcohols have been studied. The catalytic activity of these material is in the order: SAPO-41> SAPO-11> SAPO-31.

IPC Code: Int. Cl.7 B01J 29/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1044-1050

 

Electrochemical oxidation of 6-thioxanthine at
pyrolytic graphite electrode

Rajendra N Goyal*, Udai P Singh & Adil A Abdullah

 

6-Thioxanthine has been studied in phosphate buffers of pH 1.2 11.0 using linear and cyclic sweep voltammetry, coulometry, controlled potential electrolysis and spectral studies. Two well-defined oxidation peaks, Ia (1e, 1H+, pH range 1.2-6.0) and IIa (8e, 8H+, pH range 1.2-11.0) are observed. A reduction peak, IIIc, is noticed in the reverse sweep.  Kinetic studies indicate that the decay of the UV- absorbing intermediate is a first order reaction. The studies show that in acidic medium, thio group of 6-thioxanthine exists as S-H, whereas in neutral and basic medium thio group is in the form of C=S. The products of electrooxidation have been characterized and a tentative EC mechanism has been suggested for the oxidation of 6-thioxanthine.

 

IPC Code: Int. Cl.7 C07B 33/00

 

 

 

Indian Journal of Chemistry

Vol. 42A, May 2004, pp. 1051-1055

 

Kinetics of reactions of o-(2,4-dinitrophenyl)indanone
oxime with cyclohexylamine, piperidine and
ethanolamine in acetonitrile

Gurudas Bhattacharjee*, Ashok Kumar Singh, Rupam Singh & Priti Gairola

 

Effect of nucleophile on the reactions of o-(2,4-dinitrophenyl) indanone oxime (DNPIO) has been studied with cyclohexylamine (CHA), ethanolamine (ETA) and piperidine (PIP) in acetonitrile at 350.1C. Reactions of DNPIO with CHA and ETA are kinetically of second order. However, the reactions with PIP are wholly base catalyzed and a third order dependence on PIP has been observed.

 

IPC Code: Int. Cl.7 C07C 251/32

 

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1056-1059

 

Kinetics and mechanism of the oxidative regeneration of carbonyl compounds from oximes by [bis(trifluoroacetoxy)iodo]benzene

Alpna Kansara, Pradeep K Sharma & Kalyan K Banerji*

 

The oxidation of several aldo- and keto-oximes by [bis(trifluoroacetoxy)iodo] benzene (TFAIB), in aqueous acetic acid exhibits first order dependence on both the oxime and TFIAB. The oxidation of ketoximes is slower than that of aldoximes. The oxidation of aliphatic oximes correlates well in terms of Pavelich-Taft dual substituent-parameter equation. The reaction constants have positive values. The low positive value of the polar reaction constant indicates a nucleophilic attack by TFIAB on the carbonyl carbon. The reaction is subject to steric hindrance by the alkyl group. A mechanism involving the formation of a cyclic activated complex in the rate-determining step has been proposed.

 

IPC Code: Int. Cl.7 C 07C 251/32

 

 

 

Indian Journal of Chemistry

 Vol. 42A, May 2004, pp. 1060-1065

 

A kinetic study of the reduction of chromium(VI) by thiourea in the absence and presence of manganese(II), cerium(IV) and ethylenediaminetetra acetic acid (EDTA)

Zaheer Khan*, Mohammad Yousuf Dar, Prabijna S S Babu & Kabir-ud-Din

 

The kinetics of reduction of Cr(VI) by thiourea has been studied spectrophotometrically in an HClO4 medium. The reaction follows overall third order kinetics, first order each in Cr(VI), thiourea and HClO4. The reaction is HClO4 catalyzed. Addition of Mn(II) and Ce(IV) ions largely decrease the reaction rate. The reaction rate is increased by addition of EDTA. The spectrophotometric study indicates that the reduction of chromium(VI) follows the sequence

where, R=reductant (thiourea). The reaction is considered to proceed through the formation of a ternary EDTA-chromium(VI)-thiourea complex which decomposes giving the reduced Cr(IV)-EDTA complex, followed by fast reduction with thiourea. The reduction products of chromium(VI) have been found to be Cr(III)-thiourea (lmax = 425 and 600 nm) and Cr(III)-EDTA (lmax = 410 and 550 nm), respectively, in the absence and presence of EDTA.

 

IPC Code: Int Cl7. Co1G 37/14

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1066-1075

 

More insight into the crystal structure of [Co(H2O)4
(4-nba)2]2H2O (4-nba=para-nitrobenzoate): An unprecedented hydrogen bonded supramolecular network

B R Srinivasan*,& Sarvesh C Sawant  & Samar K Das

 

The title complex tetra-aquobis(para-nitrobenzoato)cobalt(II) dihydrate 1 crystallizes in the triclinic space group Pwith the following unit cell dimensions for C14H20N2CoO14 (M=499.25) a=7.227(5) , b=7.341(5) , c=10.604(5) , a = 85.884(5)o b = 87.938(5)o g = 60.178(5) o V = 486.8(5) 3, Z=1, Dc=1.703 g.cm-3. In 1, the para-nitrobenzoate anion functions as a monodentate ligand and the Co(II) metal is located on a centre of inversion. The central metal is bound by four oxygen atoms of four water ligands, which lie on a square plane and two monodentate nitrobenzoate ligands, which are trans to each other, complete a distorted octahedron around cobalt. The oxygen atom of the nitro group of the para-nitrobenzoate forms hydrogen bonds (H acceptor bonds) with a H atom of the coordinated water on an adjacent Co thus linking the complex in a chain. These chains are further linked by hydrogen bonding which use the crystal water. This gives rise to an unprecedented hydrogen bonded supramolecular network. The title complex can be fully dehydrated to the corresponding anhydrous complex, which in turn can be rehydrated to 1. The synthesis, spectroscopic, thermal and X-ray structural characterization of the title complex 1 are described.

 

IPC Code: Int. Cl.7 C 01G 51/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1076-1082

 

Iron(II) reduction, protonation and iron(III) equilibria of
some chlorocobalt(III)dioxime complexes

A Dayalan* & A Xavier

 

Cobalt(III) complexes of the type [Co(dpgH)2(s-py)Cl],where dpgH=diphenylethanedione dioximate, s-py= pyridine (py) or a substituted pyridine like nicotinic acid(nic-COOH), quinoline(Q) or 8-hydroxy quinoline(Q-OH) have been prepared and their iron(II) reductions have been studied at 300 nm under pseudo-first order conditions with an excess of the reductant in DMSO-H2O (10% v/v) medium at 270.1 C and I=0.25 M (LiClO4) in the [H+] range 0.01 - 0.1M. An inverse acid dependence on the rate of reduction of the complexes indicates the oxime bridged inner-sphere reduction with equilibria involving H+. Hence, the second order rate constants and the rate coefficients have been determined considering the protonation equilibrium at the oxime oxygen. A mixture of the complex and H+ shows an increase in absorption in the region 250-350 nm only; whereas, a mixture of the complex, H+ and iron(III) an intense absorption in another region also viz.., 375-500 nm.The equilibrium constants for equilibria involving H+ and the cobalt(III) complexes and for equilibria involving H+, iron(III) and the cobalt(III) complexes have been evaluated by pH titrations and measuring the absorbance of the reaction mixtures in the region 375-500 nm, respectively.

 

IPC Code: Int. Cl.7 C01 G 51/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, May 2004, pp. 1083-1087

 

Diamino-functionalized mesoporous molecular sieve anchoring V(IV) and Mo(VI) complexes
as catalyst for alkene epoxidation

 Hengquan Yang, Gaoyong Zhang*, Xinlin Hong & Yinyan Zhu

 

The novel hybrid catalysts have been prepared by anchoring homogeneous catalysts VO(acac)2 and MoO2(acac)2 onto the diamino-functionalized mesoporous molecular HMS achieved by silylation of mesoporous sieve HMS with 3-[(2-aminoethyl)-amino]-propyldimethoxymethylsilane. The developed hybrid catalysts demonstrate high activity as their homogeneous counterparts for cyclohexene epoxidation with t-butyl hydroperoxide as oxidant. The yield of cyclohexene oxide is found to be 74.2% for the catalyst NMS-AASP-Mo, and more than 80% of selectivity has been obtained for all the developed hybrid catalysts. The catalysts exhibit easy recovery, and the metal leaching is found to be less than 6% after two runs. The catalysts have been characterized with N2 physical adsorption, X-ray powder diffraction, FT-IR spectrum, DRUV-vis spectrum and ICP-AES.

 

IPC Code: Int. Cl.7 B01J 23/16; B01J 29/076

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1088-1091

 

Spectroscopic and surface studies of catalytically active Zn1-xMnxFe2O4 (X= 0, 0.25, 0.50, 0.75 and 1)
ferrospinel systems

A Radheshyam, Reena Dwivedi, Vanga S Reddy, R Prasad* , Tushar Banerjee  & Pankaj Patidar

 

Zn-Mn ferrospinel systems have been characterized by ESR, X-ray diffraction, FTIR, BET surface area and ammonia desorption methods. It has been observed that ESR spectra of systems  possessing high x values are highly magnetic in nature. Distortion of the system is also observed with increasing Mn content in the samples. The g-values are in the range of 2.11410 - 2.11455.  XRD pattern confirms FCC lattice for the system. XRD particle size decreases with increasing Mn content in the system. Two broad bands appearing at 700 and 500 cm-1 in the FTIR spectra of spinels are ascribed to M-O stretching frequency of tetrahedral and octahedral sites respectively. All catalysts show weak, medium and strong acidic sites corresponding to ammonia desorption in different temperature ranges 423-523, 523-623 and 623-723 K. The acidity and surface area increases with increasing Mn content of the system. These findings have been correlated with the catalytic activity of spinels in the alkylation of few aromatic compounds.

 

IPC Code: Int. Cl.7 B01 J 23/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, May 2004, pp. 1092-1094

 

Solvation models in the reaction between
benzyl bromide and diphenyl amine

S Ranga Reddy & P Manikyamba*

 

The effect of different protic and dipolar aprotic solvents on the rate of the reaction between benzyl bromide and diphenyl amine has been studied. Correlation of the rate constants with different solvent parameters indicates that the polarity, nucleophilicity and hydrogen bond donor ability of the solvent simultaneously influence the rate and the solvation of the reactants and the transition state is due to these properties of the solvent.

 

 

 

Indian Journal of Chemistry

 Vol. 43A, May 2004, pp. 1095-1098

 

Determination of amino acids separated by
micellar electrokinetic chromatography
after pre-column derivatization with o-phthalaldehyde

 A Durgbanshi, S Sharma, M Shelke, D Bose, A Asthana & S K Sanghi*

 

A simple, sensitive and rapid analytical method has been developed for the determination of amino acids separated by micellar electrokinetic chromatography after pre-column derivatization with o-phthalaldehyde. The separated amino acids have been detected using ultraviolet as well as electrochemical detection modes. The OPA derivatized amino acids have been separated on a 75 mm (internal diameter) fused silica capillary. UV detection has been performed at 220 and 335 nm respectively, while electrochemical detection has been done at 500 mV against Ag/AgCl reference electrode. Optimum separation has been achieved using an applied voltage of 28 kV. Enhanced sensitivity is achieved with the electrochemical detection mode. The standard curve of amino acids is found to be linear in the range of 10-5 to 510-7 M. The % relative standard deviation for retention time is found to be less than 0.4 while for peak height and peak area it is within 1%.

 

IPC Code: Int.Cl.7 B01D 15/08

 

 

 

Indian Journal of Chemistry

 Vol. 42A, May 2004, pp. 1099-1101

 

Study of the interaction of butyl rodamine B with DNA
and the determination of DNA based on
resonance light scattering measurements

Gong-wu Song*, Zhao-xia Cai & Ling Li

 

A new method for determination of nucleic acids in aqueous solutions has been developed, based on the enhancement of resonance light scattering (RLS) of butyl rhodamine B (BRB) by nucleic acids under acidic condition at 400 nm. The intensity of resonance light scattering is found to be proportional to the DNA concentration in the linear range 5.8~2 688 ng.mL-1, and the determination limit (3σ) is 5.8 ngmL-1. The method is highly sensitive, rapid, simple (one step assay), and reproducible and has been successfully applied for determination of DNA in synthetic samples. Under the experimental conditions, there is little interference from proteins, nucleosides and most metal ions.

IPC Code: Int. Cl.7 C07H 21/00, G 01J 3/44

 

 

 

 

Indian Journal of Chemistry

Vol. 42A, May 2004, pp. 1102-1105

 

Crystallographic and spectroscopic studies of
luminescent copper(I) complex [(PPh3)2Cu(S2COMe)] Insertion reaction of carbon disulfide

Zhao Dong*, Li Guanliang, Zhao Liang, Zhang Chuanjian & Sun Yuan

 

The luminescent copper(I) complex [(PPh3)2Cu(S2COMe)] has been obtained by treating [(PPh3)2Cu(NO3)] with carbon bisulfide in a mixed solvent of methanol and dichloromethane at room temperature. The complex has been characterized by physicochemical and spectroscopic methods, and has been found to exhibit photoluminescence behaviour at room temperature. The structure of the complex has been determined by X-ray structure analysis. The crystal is orthorhombic, space group P212121, with parameters a = 9.513(2) , b = 18.075(4) , c = 19.968 , V = 3433.4(12) 3, Z = 4, F(000) = 1440, D(calcd.) = 1.345 Mg/m3, μ = 0.880 mm-1, R = 0.0487, Rw = 0.0935. The results show that PPh3 coordinates as monodentate ligand to the copper(I) atoms, and MeCOS2- behaves as a bidentate ligand in the prepared complex. Hence, each copper atom has a CuP2S2 tetrahedron coordination skeleton.

 

IPC Code: Int. Cl.7 C09K 11/58

 

 

 

Indian Journal of Chemistry

 Vol. 43A, May 2004, pp. 1106-1108

 

Spectral and thermal characterization of
new biomimetic polydentate amide ligands

Bhagwan S Garg*, Meenu Sarbhai & Deo Nandan Kumar

 

Complexes of manganese(II) and nickel(II) with N,N-bis(3-carboxy-1-oxopropanyl)-1, 2-ethylenediamine (C10H16N2O6,L1), N, N-bis(3-carboxy-1-oxopropanyl)-1, 2-phenylenediamine (C14H16N2O6,L2), N,N-bis(2-carboxy-1-oxophenelenyl)-1, 2-phenylenediamine (C22H16N2O6,L3) and N,N-bis(3-carboxy-1-oxoprop-2-enyl)-1, 2-phenylenediamine (C14H12N2O6,L4) have been prepared and characterized by elemental analysis, vibrational spectra, magnetic susceptibility measurements, electronic spectra and thermal studies. Vibrational spectra indicates coordination of amide and carboxylate oxygens of the ligands giving a MO4 chromophore. Electronic spectra support square planar geometry around nickel(II) and tetrahedral around manganese(II). NiL1 complex has the maximum activation energy and NiL2 complex has the minimum activation energy.

 

IPC Code: Int Cl7. 01G 45/00; C01G 53/00

 

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1109-1111

 

Synthesis and crystal structure of triphenyltin diphenylthiocarbazone

Rufen Zhang,  Feng Li & Chunlin Ma*

 

The compound (Ph3SnSN4C13H11) has been prepared by the reaction of triphenyltin chloride with diphenylthiocarbazone in sodium alcoholic. Its structure has been determined with IR, 1H NMR and X-ray crystallography. It crystallizes in the monoclinic, space group P-1, a=8.608(2) , b=11.991 (3) , c=13.760(3) , α=98.912(3) , b=94.961(4) , γ=94.086(4) , Z=2, V=1392.7 (6) 3, Dc=1.443 g/cm3, m=1.019 mm-1, F(000)=612, R1=0.0639, wR2=0.0593. The central Sn atom is distorted trigonal bipyramid.

 

IPC Code: Int. Cl.7 C 01G 19/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1112-1118

 

Synthesis, characterisation and redox behaviour of mixed ligand complexes of osmium(II/III/IV)-phosphines

Habibar Chowdhury, Jaya Banerjee, Sk Hafijur Rahaman, Doyel Bose & Barindra Kumar Ghosh*

 

The reaction of [OsX2L2] [X = Cl or Br; L = 2-(m-tolylazo)pyridine (tapy), 1; L = quinolin-8-olate (oxin), 2] with tertiary phosphine (PR3 = PPh3 or PPh2Me) bases in boiling aqueous alcohol affords complexes of the types [OsX(PR3)L2]Z+ (L = tapy, Z = 1, 3; L = oxin, Z = 0, 5) and [Os(PR3)2L2]n+ (L = tapy, n = 2, 4; L = oxin, n = 0, 6), which when charged isolated as their perchlorates. The osmium(IV) counterparts [OsX(PR3)-(oxin)2]1+ (7) and osmium(III) species [Os(PR3)2(oxin)2]1+ (8) of [OsX(PR3)(oxin)2] (5) and [Os(PR3)2(oxin)2] (6), respectively are also stable enough for isolation by oxidation with cerium(IV). The new complexes have been characterized by spectroscopic, magnetic, electrochemical and other physicochemical results. Using 1H NMR results (dMe of tapy/PPh2Me) in selected cases the stereochemistry of OsL2 fragment in these mixed L-PR3 complexes has been proposed. The diamagnetic osmium(II) complexes display a number of spin-allowed and spin-forbidden MLCT transitions whereas LMCT bands are seen in paramagnetic osmium(III) and osmium(IV) compounds. All the complexes are electroactive and exhibit osmium(III)-osmium(II) response in MeCN solutions; additionally, oxin complexes show osmium(IV)-osmium(III) couple within accessible potential window. The stability of metal oxidation levels is discussed in terms of the electrochemical results and correlated to the p-acceptor strengths of these ligands.

 

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

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1119-1122

 

Synthesis, characterisation and X-ray
structure of a mononuclear zinc(II)azido complex
containing tetradentate schiff base

Jaya Banerjee, Doyel Bose, Sk Hafijur Rahaman, Rosa D Bailey Walsh, M J Zaworotko &
Barindra K Ghosh*

 

The synthesis, characterisation and single crystal X-ray structural analysis of [Zn(bnbzpy)(N3)]ClO4 (1) [bnbzpy = N,N-(bis(pyridin-2-yl)benzylidene)butane-1,4-diamine] have been described. X-ray diffraction study has been made for the exact definition of the coordination sphere. Structural analysis reveals that the zinc(II) centre in mononuclear 1 is in a distorted trigonal bipyramidal ZnN5 environment ligated by four N atoms of the organic blocker and the terminal azide. The tetradentate chelator is folded in the butylenic part.

 

IPCCode: Int.Cl.7 C01G 9/00

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1123-1125

 

Synthesis and characterization of 6,7 and 8-coordinate monomeric complexes of tungsten obtained from reaction of [W(CO)3(MeCN)3] with pyridine-2-thiol (pySH) and PPh3

 Anjumanara, Noorjahan Begum, Farzana K Camellia, Shariff E Kabir* & Kalipada Kundu*

 

Complexes [W(CO)4(PPh3)2] 1, [W(CO)4(pySH)(PPh3)] 2, [W(CO)2(pyS)2(PPh3)] 3 and [W(pyS)4] 4 have been obtained from the reaction of [W(CO)3(MeCN)3] with pyridine-2-thiol (pySH) and PPh3 in refluxing THF. 1 and 2 are normal 6-coordinate complexes but 3 and 4 are unusual 7 and 8-coordinate complexes, respectively. The complexes have been characterized by IR, 1H and 31P{1H}NMR, mass spectra and elemental analysis.

 

IPC Code: Int.Cl7. C01G 41/00

 

 

 

Indian Journal of Chemistry

 Vol. 43A, May 2004, pp. 1126-1130

 

Polymeric and binuclear monomeric Mn(II) chelates of some multidentate azo compounds derived from b-diketones

K Y El-Baradie*, R M Issa & M Gaber

 

A new series of polymeric and binuclear Mn(II) chelates have been synthesized and characterized by elemental analysis, electronic, IR , and EPR spectra. The room temperature magnetic susceptibility and the spectral analysis of the two types of complexes indicate a markedly different behaviour. Binuclear complexes are 1:1 electrolyte whereas polymeric mononuclear Mn(II) complexes are non-conducting.

 

IPC Code: Int. Cl7. C07C 245/02

 

 

 

 

Indian Journal of Chemistry

Vol. 42A, May 2004, pp. 1131-1133

 

Synthesis and anti-HIV activity of
metal complexes of SRR-SB3

Minu G Bhowon* & B S Jhaumeer Laulloo

 

The disulphide diamide SRR-SB3 (7-methyl-6,7,8,9-tetrahydrodibenzo [c,k] [1,2,6,9] dithiadiazacyclododecine-5-10-dione) and its metal complexes have been synthesized and characterised by elemental analyses, IR, 1H{13C} NMR, mass spectra and magnetic moment data. The complexation of the ligand SRR-SB3 with several metal ions such as ruthenium(III), cobalt(II), iron(III), lead(II), copper(II), nickel(II), zinc(II), manganese(II) and palladium(II) chloride have been studied. The metal ions, Ru and Zn are found to complex successfully with SRR-SB3. The metal complexes have been found to inhibit the replication of HIV-1 (IIIB) and HIV-2 (ROD) strains using MT-4 cells with a selectivity index ranging from 5 to 27.

 

IPC Code: Int. Cl.7 C07F 15/02, C 07F 17/02

 

 

 

Indian Journal of Chemistry

Vol. 43A, May 2004, pp. 1134-1138

 

Synthesis and characterization of dioxarsolanes and -arsenanes complexes using O,O-alkylene dithiophosphate

Romesh Chander, B L Kalsotra & Sushil K Pandey*

 

O,O-alkylene dithiophosphato derivatives of arsenic(III), [OGOAsS2POGO] have been synthesized in quantitative yield by the reaction of 2-chloro-1,3,2-dioxarsolanes and -arsenanes, [OGOAsCl] (G= -CH2CH2-, -CHMeCH2-, -CH2CH2CH2- or -CHMeCH2CMe2-), with ammonium salt of O,O-alkylene dithiophosphoric acids, [NH4S2POGO] (G= -CH2CMe2CH2-, -CH2CEt2CH2-, -CHMeCH2CMe2-, -CMe2CMe2- or -CHMeCHMe-), under anhydrous condition. These yellow viscous complexes have been characterized by elemental analysis, molecular weight determinations and spectroscopic studies such as IR and NMR (1H, 13C and 31P). On the basis of these studies, a bidentate mode of bonding of dithio moieties with arsenic has been suggested leading to a trigonal bipyramidal geometry around arsenic(III) atom in the complexes.

 

 

IPC Code: Int.Cl7. C01G 28/00