Indian Journal of Chemistry

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

 

VOLUME 41A

NUMBER 12

DECEMBER 2002

CONTENTS

Rapid Communication

 

2447

 

A new decavanadate salt incorporating both inorganic and organic cations

 

 

 

Bharat Baruah & Animesh Chakravorty*

 

 

The structure of the orange-red salt, [Cs2(H2O)2(tea)2H2V10O28] synthesized from V2O5, aqueous H2O2, [tea] [Cl] and CsCl consists of an unusual array of centrosymmetric H2V10O284- units strongly interlinked by cesium ions which are chelated by the triethanolammonium cation (tea+).

Papers

 

2450

 

On the electronic structures of quasi-one-dimensional model superlattices of type-I

 

 

Parul Bhargava & A K Bakhshi*

 

 

2456

 

Ground and excited state interaction between luminol and ethylene trithiocarbonate: A fluorescence quenching study

 

D Banerjee, A Mandal & S Mukherjee*

 

 

 

The absorption spectral change and fluorescence quenching of luminol due to the interaction with ethylene trithiocarbonate both in the ground and excited states have been investigated using steady state and time-correlated single photon counting techniques.

 

 

2462

 

Study on transport behaviour of Bi(NO3)3 in water + DMF/DMSO

 

 

J Ishwara Bhat* & T N Sreelatha

 

 

 

Limiting molar conductance of Bi(NO3)3 has been determined at all compositions of DMF and DMSO with water at different temperatures. Solvation number of the species has been calculated and found to be fractional indicating the formation of solvent separated ion-pair in the system under existing conditions.

 

2468

 

 

 

Studies on kinetics and mechanism of iridium(III) catalysed cerium(IV) oxidation of d-mannitol and d-glucose in aqueous acid media

 

 

Aparna Roy & Asim K Das*

 

 

 

 

 

 

 

2475

 

Kinetics of complex formation reactions of chloromethyl(aquo)cobaloxime complex with cyanide and imidazoles

 

 

D Sudarshan Reddy, A Rajeshwar Rao &

S Satyanarayana*

 

 

 

2482

 

Kinetics and mechanism of palladium(II) catalysed oxidation of some a-aminoacids by chloramine-T in perchloric acid

 

 

 

 

 

 

Neeti Grover, Neelu Kambo & Santosh K Upadhyay*

 

 

 

 

 

               

   k6

(X) + (RNH2Cl)+     R¢CH=N+H2 +PdCl2+RNH2 + CO2

H2O

 

                                                R¢CHO + NH4+

 

 

2489

 

Synthesis of thiosemicarbazone derivative of 2-OH naphthaldehyde and its application in synergistic extraction of gold (III)

 

S Banerjee & S Basu*

 

 

 

Thiosemicarbazone derivative of 2-OH naphthaldehyde has been synthesised by the reaction of 2-OH naphthaldehyde and thiosemicarbazide and characterised. The synergistic studies have been performed at pH = 6.5 and the effect of various diluents on the extent of synergism of Au3+ by this ligand have also been studied.

 

 

2494

 

Synthesis and characterization of polystyrene supported coordination compounds of dibasic tridentate Schiff base

 

 

 

 

 

 

 

 

 

D Kumar*, P K Gupta & A Syamal

 

 

 

Notes

 

2500

 

The interaction potential of helium–neon

 

 

 

 

Elaheh K Goharshadi* & Majid Moinossadati

 

 

 

The pair potential energy function of He-Ne has been determined using inversion of the experimentally reduced viscosity collision integrals obtained from the corresponding-states correlation. The potential has been used to predict the viscosity and diffusion coefficients of He-Ne binary mixture.

 

 

2503

 

Enantioselective Michael addition and Henry reaction catalyzed by a new heterobimetallic aluminum-lithium complex derived from (+)-2,3-O-isoproylidine threitol

 

Ch V Rajasekhar & H Maheswaran*

 

 

Heterobimetallic catalyst obtained by the reaction of LiAlH4 with (+)-2,3-O-isoproylidine threitol promotes asymmetric Michael reaction as well as Henry reaction.

 

2507

 

Partial molar volume and ultrasonic studies of cobalt (III) complexes in aqueous and binary aqueous media at different temperatures

 

 

U N Dash*, G S Roy & S Mohanty

 

 

 

Studies of apparent molar volume have been made in the solutions cobalt (III) complexes containing glycine, a-alanine and b-alanine in water, water+acetone and water+alcohol  mixtures . The results are discussed in the light of ion-ion and ion-solvent interactions and of structural effects of the solvent in solutions.

 

2514

 

 

 

 

 

 

 

 

Kinetics and mechanism of acid dissociation of cobalt(II) complex of 1,10-phenanthroline tetradentate diamine ligands

 

 

 

 

 

 

Hong-Wei Sun, Hua-Kuan Lin*, Zhi-Fen Zhou, Guang-Hua Zhao, Shou-Rong Zhu, Xun-Cheng Su & Yun-Ti Chen

 

 

2518

 

Kinetics of condensation of aryl isothio-cyanates with aryl amines

 

 

Late G Y Pathrikar, S P Bondge, A S Burungale, V E Bhingolikar, R D Ingle & R A Mane*

 

 

 

The kinetics of condensation of aryl isothiocyanates with aryl amines in non-aqueous medium have been investigated. The condensation reaction is first order each in [amines] and  [isothiocynate].

 

2522

 

Kinetics of direct bimolecular substitution reaction of a cis-platinum(II) complex with piperidine in water/alcohol mixtures

 

 

M R Gholami & B A Talebi*

 

 

 

 

 

 

 

 

 

 

 

Kinetics of direct bimolecular substitution reaction of cis-[Pt(SEt2)2Cl2] with piperidine has been  studied in water-methanol, -ethanol and -2-propanol mixtures.The  modelling studies  show that dipolarity/polarizability parameter is more effective than the others in this reaction.

 

2526

 

Synthesis, characterization and ion exchange properties of zirconium(IV) triethylammonium phosphate

 

 

Dhruv K Singh*, Shalini Singh & Bhavana Srivastava

 

 

An ion exchanger based on zirconium(IV) triethylammonium phosphate  has been synthesized. Some analytically useful separations of metal ions have been achieved on small column of this exchanger.

 

2530

 

 

 

 

 

 

 

Synthesis and crystal structure of ternary complex [Cu(phen)(sal)](ClO4)

 

 

 

Tian-Fu Liu, Hua-Kuan Lin*, Shou-Rong Zhu, Zhong-Ming Wang, Hong-Gen Wang, Xue-Bing Leng & Yun-Ti Chen

 

 

 

2533

 

The X-ray structure of bis(salicylidene)-4,4¢-biphenylenediamine

 

 

 

 

 

 

Lallan Mishra* , Kumari Bindu &

Lawrence C Nathan

 

 

 

2536

 

Synthetic, spectroscopic and biocidal aspects of sixteen to twenty two-membered tetraazamacrocyclic complexes of tin(II)

 

 

 

 

Ashu Chaudhary , R V Singh & Anita Phor*

 

 

 

2540

 

Synthesis and spectroscopic characterization of molybdenum(0) and molybdenum(II) carbonyl benzophenoneazine complexes

 

 

 

M A Affan*, Ramli bin Hitam & Mustaffa bin Shamsuddin

 

 

 

                      

 

 

2544

 

Synthesis and characterization of lanthanide complexes of 1-phenyl-3-methyl-5-hydroxy-4-pyrazolyl-phenyl ketone-2′-picolinoyl hydra-zone

 

 

 

B T Thaker * & Chetan K Modi

 

 

 

 

 

2548

 

Trace level determination of bromide in presence of large concentration of chloride by differential pulse polarography

 

 

P Sharma* & Rakesh Sharma

 

 

 

The optimum conditions for the determination of bromide at low concentrations has been developed employing differential pulse polarography.

 

2551

 

Adsorption of oxine and its derivatives on granular activated carbon

 

 

Veena Mustoor & G S Natarajan*

 

 

The adsorption of 8-hydroxyquinoline and some of its derivatives on granular activated carbon, F-400 sample has been studied. The surface area calculated on the basis of monolayer formation of these adsorbates has been correlated with structure of the oxines.

 

 

2555

 

 

Announcement

 

2557

 

 

Annual Index

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2447-2449

A new decavanadate salt incorporating both inorganic and organic cations

Bharat Baruah  & Animesh Chakravorty*

 

The title salt, [Cs2(H2O)2(tea)2H2V10O28] has been isolated by reacting a solution of V2O5 in aqueous H2O2 with [tea][Cl] and CsCl (tea+ is triethanolammonium cation). The structure of the salt consists of an unusual three-dimensional array of centrosymmetric H2V10O284- units (protonation sites consistent with bond valence sums) strongly interlinked by cesium ions which are chelated by the tea+ ligand.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2450-2455

 

On the electronic structures of quasi-one-dimensional model superlattices of type-I

 

Parul Bhargava & A K Bakhshi*

The electronic structures of the three different quasi-one-dimensional model superlattices (copolymers)(AmBn)x belonging to the class of type-I have been calculated in the tight-binding approximation using the direct numerical approach. For each of the three systems, component A is the same while component B, though having same band widths and band gap, differs in its alignment with respect to A. The trends in their electronic structures as a function of (i) composition (m/n),
(ii) block sizes m and n and (iii) arrangement of units (periodic or aperiodic) in the copolymer chain are discussed. The results obtained are important guidelines for designing copolymers with tailor-made conduction properties.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2456-2461

 

Ground and excited state interaction between luminol and ethylene trithiocarbonate: A fluorescence quenching study

 

D Banerjee, A Mandal & S Mukherjee

The absorption spectral change and fluorescence quenching of luminol (3-aminophthalhydrazide) due to the interaction with ethylene trithiocarbonate (ETTC) both in the ground and excited states have been investigated using steady state and time-correlated single photon counting techniques. The complex formation in the ground state is assumed to explain the high value of bimolecular rate constant and is consistent with positive curvatures in the Stern-Volmer (S-V) plots. The equilibrium constant for the complex formation due to the hydrogen bonding interaction has been calculated from absorption spectral changes. The bimolecular rate constants in hydrogen bonding solvents have been found to be quite higher than those obtained in nonpolar and weakly polar solvents. It is proposed that interaction in the ground state is mainly between luminol and hydrogen bonding solvent molecules. A plausible explanation of the quenching mechanism has been discussed on the basis of hydrogen bonding interaction between the colliding species.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2462-2467

Study on transport behaviour of Bi(NO3)3 in water + DMF/DMSO

 

J Ishwara Bhat* & T N Sreelatha

 

Bismuth nitrate is subjected to electrical conductivity studies in water + DMF and water + DMSO at four different temperatures. Limiting molar conductance of Bi(NO3)3 has been determined at all compositions of DMF and DMSO with water and at different temperatures. Limiting conductance is found to be less in water + DMF mixture than in water + DMSO mixture. Large value of limiting conductance is interpreted due to the release of proton from the co-solvent on account of the action of Lewis acid (Bi3+) on DMF or DMSO in the presence of water. Dissociation and association constants have been calculated. Exothermic nature of the system is supported by the values of thermodynamics of association as well as solvation. Preferential solvation of the cation by the non-aqueous solvent has been observed. Solvation number of the species has been calculated and found to be fractional indicating the formation of solvent separated ion-pair in the system under existing conditions.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2468-2474

 

Studies on kinetics and mechanism of iridium(III) catalysed cerium(IV) oxidation of d-mannitol and d-glucose in aqueous acid media

 

Aparna Roy & Asim K Das*

 

The kinetics and mechanism of Ce(IV) oxidation of d-mannitol and d-glucose in aqueous H2SO4 media in the presence and absence of Ir(III) have been studied and compared under the conditions, [S]T >>[Ce(IV)]T>>[Ir]T, where [S]T gives the total substrate (d-mannitol or d-glucose) concentration and [Ir]T denotes the total concentration of Ir(III) catalyst added. Ir(III) has been found to catalyse the title reactions very efficiently even at trace concentration (ca.10–6 to 10–7 mol dm–3). Under the kinetic conditions, both the uncatalysed and catalysed reactions take place simultaneously. The overall process shows a first order dependence on [Ce(IV)] and [S]T . The catalytic path is first order in [Ir]T. The catalytic path is suggested to involve the Ir(III)/Ir(IV) catalytic cycle. The process is acid catalysed and inhibited by [HSO4-]. From the HSO4- dependence, both Ce(SO4)2+ and Ce(SO4)2 have been found kinetically active in d-mannitol oxidation while in d-glucose oxidation Ce(SO4)2 is the main kinetically active species under comparable conditions. The different kinetic parameters for both the Ir(III) catalysed and uncatalysed paths have been estimated.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2475-2481


Kinetics of complex formation reactions of chloromethyl(aquo)cobaloxime complex with cyanide and imidazoles

D Sudarshan Reddy, A Rajeshwar Rao & S Satyanarayana*

Formation constants have been determined for the reaction of ClCH2Co(DH)2OH2 with CN- and different imidazole based nucleophiles as a function of pH. The kinetics of this reaction has been studied as a function of entering ligand concentration at a fixed pH and as a function of pH at a fixed concentration of the entering ligand. Dissociation reaction has also been studied as a function of pH. Bonding and kinetic data have been interpreted based on the basicity, bulkiness (steric crowd) of the entering ligand and HSAB principle. The soft ligand CN- binds very strongly. To compare the rate constants of the entering ligands, pH independent second order rate constants have been calculated.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2482-2488

 

Kinetics and mechanism of palladium(II) catalysed oxidation of some

a-aminoacids by chloramine-T in perchloric acid

 

Neeti Grover, Neelu Kambo & Santosh K Upadhyay*

 

The kinetics of palladium(II) catalysed oxidation of some a-aminoacids (AA), viz., glycine (Gly), alanine(Ala), phenylalanine (Ph-Ala) and valine(Val) by chloramine-T (CAT) in HClO4 medium have been investigated. The following rate law is observed on the basis of kinetic results,

 

k[H+] [AA] [CAT] [Cl-] [Catalyst]

Rate a

{1 + k¢ [H+]} {1+ k¢¢ [Cl-] + k¢¢¢ [AA]}

 

where k, k¢, k¢¢ and k¢¢¢ are constants. However, the rate of oxidation of Gly follows a second order dependence of rate in [CAT]. The corresponding aldehydes have been observed as the major oxidation prouducts of the aminoacids under the kinetic conditions. A spectrophotometric evidence for the formation of 1:1 complex between PdII and AA has been observed and a mechanism consistent with kinetic data has been proposed and discussed.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2489-2493

 

 

Synthesis of thiosemicarbazone derivative of 2-OH naphthaldehyde and its application in synergistic extraction of gold (III)

 

S Banerjee & S Basu*

A widely useful class of chelating ligand, i.e., thiosemicarbazone derivative of 2-OH naphthaldehyde, has been synthesised by the reaction of 2-OH naphthaldehyde and thiosemicarbazide and characterised. Application of this ligand in synergistic extraction of Au(III), from hydrochloric acid medium in presence of amine donors like TOA, Adogen 464, Amberlite LA-2 and some phosphorus oxide donors like TOPO, bis(2-ethyl hexyl) phosphonate, TBPO, TPPO and TBP, using methyl isobutyl ketone as the solvent has been studied and log kex values for binary organic phase [Au(A)(Cl)2] found to be 11.89, which is by far the largest among the corresponding values known for other thiosemicarbazones. The overall equilibrium (log K) constants have been calculated for all the ternary adducts, [Au(A)(Cl)2S], where S represents donor and A the ligand. The synergistic studies have been performed at pH = 6.5 and the effect of various diluents on the extent of synergism of Au3+ by this ligand have also been studied.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2494-2499

 

Synthesis and characterization of polystyrene supported coordination compounds of dibasic tridentate Schiff base

D Kumar*, P K Gupta & A Syamal

Several polystyrene supported coordination compounds of the types, PSCH2–LM×DMF (M=Cu, Zn, Cd, MoO2 and UO2), PSCH2–LFeCl×2DMF, PSCH2–LZr(OH)2×2DMF and PSCH2–LM×3DMF(M=Mn, Co and Ni) have been synthesized and characterized by elemental analyses, IR, reflectance, ESR spectral and magnetic susceptibility measurements. The Mn(II), Fe(III), Co(II), Ni(II), MoO2(VI) and UO2(VI) compounds have an octahedral structure, Cu(II) compound is square planar, Zn(II) and Cd(II) compounds are tetrahedral, while Zr(IV) compound is pentagonal-bipyramidal. The compounds, PSCH2–LM×3DMF(M=Mn, Co and Ni), PSCH2–LFeCl×2DMF and PSCH2–LCu×DMF are paramagnetic, while PSCH2–LM×DMF(M=Cd, MoO2, Zn and UO2) and PSCH2–LZr(OH)2×2DMF are diamagnetic. PSCH2–LH2 behaves as tridentate(ONO donor) dibasic in these compounds. The structures of the compounds are comparable with the corresponding coordination compounds of the non-anchored Schiff base.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2500-2502

 

The interaction potential of helium–neon

 

Elaheh K. Goharshadi* & Majid Moinossadati

The pair potential energy function of He-Ne has been determined using inversion of the experimentally reduced viscosity collision integrals obtained from the corresponding-states correlation. A comparison of the potential with the previously determined potential is made. The potential has been used to predict the viscosity and diffusion coefficients of He-Ne binary mixture and they are found to be in a good agreement with the experiment.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2503-2506

Enantioselective Michael addition and Henry reaction catalyzed by a new heterobimetallic aluminum-lithium complex derived from (+)-2,3-O-isoproylidine threitol

CH V Rajasekhar & H Maheswaran*

 

A heterobimetallic catalyst obtained by the reaction of LiAlH4 with (+)-2,3-O-isoproylidine threitol promotes asymmetric Michael reaction (between malonic esters, and thiophenols to cyclic enones) as well as Henry reaction (between aliphatic and aromatic aldehydes and nitromethane) with excellent yields albeit low enantiomeric excesses.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2507-2513

Partial molar volume and ultrasonic studies of cobalt (III) complexes in aqueous and binary aqueous media at different temperatures

 

U N Dash*, G S Roy & S Mohanty

 

Studies of apparent molar volume have been made in the solutions of trans-bis (1,2-diaminoethane) (amino-carboxylato) halogeno cobalt (III) complexes containing the carboxylato-bonded aminoacids, e.g. glycine, a-alanine and b-alanine in water, water+acetone (5, 10 & 20 wt %) and water+alcohol (5 wt % each of methanol, ethanol and n-propanol) mixtures at 298.15, 303.15, 308.15 and 313.15 K to evaluate apparent molar properties. Studies of ultrasonic velocity have also been made for the solutions of these complexes in these solvents at 303.15, 308.15 and 313.15 K to evaluate various acoustic parameters. The results are discussed in the light of ion-ion and ion-solvent interactions and of structural effects of the solvent in solutions.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2514-2517

 

Kinetics and mechanism of acid dissociation of cobalt(II) complex of 1,10-phenanthroline tetradentate diamine ligands

Hongwei Sun, Huakuan Lin*, Zhifen Zhou, Guanghua Zhao, Shourong Zhu, Xuncheng Su & Yunti Chen

 

The dissociation kinetics of cobalt(II) complex of 1,10-phenanthroline tetradentate diamine ligands have been studied using a stopped-flow spectrophotometer in 6.6´10-3~0.5 mol·dm-3 HCl (I=0.5 mol·dm-3 HCl+NaCl) over a range of temperature. The dissociation rate follows the law kobs=kK2[H+]/(1+K2[H+]). The acid-assisted dissociation can be rationalized in terms of a four-step kinetic process involving two rapid pre-equilibrium protonations and rate-determining cleavage of the Co(II)-N(phenanthroline) bond. The temperature dependence of the rate and equilibrium constants have been determined and the appropriate thermodynamic parameters obtained. Steric effects in the dissociation kinetics have been discussed and the linear relationship between DH¹ and DS¹ has been found.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2518-2521

 

Kinetics of condensation of aryl isothio-cyanates with aryl amines

Late G Y Pathrikar, S P Bondge, A S Burungale, V E Bhingolikar, R D Ingle & R A Mane*

The kinetics of condensation of aryl isothiocyanates with aryl amines in non-aqueous medium have been investigated. The condensation reaction is first order each in [amines] and  [isothiocynate]. The effect of substituents on the rate of condensation and the thermodynamic parameters are evaluated. The reaction products have been  isolated and characterized as asymmetric thiocarbamides and a probable mechanism of the condensation proposed.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2522-2525

 

Kinetics of direct bimolecular substitution reaction of a cis-platinum(II) complex with piperidine in water/alcohol mixtures

 

M R Gholami & B A Talebi*

 

 

Kinetics of direct bimolecular substitution reaction of cis-[Pt(SEt2)2Cl2] with piperidine has been  studied in water-methanol, -ethanol and –2-propanol mixtures. Modeling of second order rate constants with respect to quasi-independent solvent parameters such as p* (dipolarity/polarizability), a(HBD acidity) & b(HBA basicity) has been carried out. Single-parameter models are not sufficient to explain the observed anomaly that occurs in the reaction rate. Because of opposite effects of p* and a, b on the reaction rate, this behaviour could be understood better using dual-parameter models of these parameters. Coefficients of parameters in final models show that dipolarity/polarizability parameter is more effective than the others in this reaction. Less negative effects of a on the reaction rate compared to b indicate that a HBD interaction could exist between the complex and protic solvents.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2526-2529

 

Synthesis, characterization and ion exchange properties of zirconium(IV) triethylammonium phosphate

 

Dhruv K Singh*, Shalini Singh & Bhavana Srivastava

A new inorganic ion exchanger based on zirconium (IV) triethylammonium phosphate (ZTEAP) has been synthesized by mixing solutions of ZrOCl2 and (C2H5)3NH.H2PO4 in different molar ratios. On the basis of higher ion exchange capacity and good appearance, sample ZTEAP5 has been chosen for detailed studies, such as chemical stability, chemical analysis, pH titration and IR analysis. Distribution coefficients of 16 metal ions have been determined in water, buffer solutions (pH 2, 4 and 6) and 0.1 mol dm-3 solutions of sodium nitrate and nitric acid. On the basis of difference in Kd values, some analytically important separations of metal ions have been achieved on small column of zirconium (IV) triethylammonium phosphate.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2530-2532

 

Synthesis and crystal of ternary complex [Cu(phen)(sal)](ClO4) (phen = 1,10-phenanthroline, sal = Salicyladehyde)

Tian-Fu Liu, Hua-Kuan Lin*, Shou-Rong Zhu, Zhong-Ming Wang, Hong-Gen Wang, Xue-Bing Leng & Yun-Ti Chen

The ternary copper (II) complex, [Cu(phen)(sal)](ClO4) (phen = 1,10-phenanthroline, sal = salicyladehyde) has been synthesized and its crystal structure determined by X-ray diffraction methods. The complex crystallizes in triclinic space group P ī, with a = 0.9163(3) nm, b = 0.9317(3) nm, c = 1.1724(4) nm, a = 96.247(6)º, b = 111.012(5)º, g = 97.113(6)º, V = 1.686 Mg/m3, Z = 2, R = 0.0454.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2533-2535

 

The X-ray structure of bis(salicylidene)-4,4¢-biphenylenediamine

Lallan Mishra* , Kumari Bindu & Lawrence C Nathan

 

The X-ray structure of the Schiff base compound bis(salicylidene)-4,4¢-biphenylenediamine (I) has been determined. Crystallographic results are: C26H20N2O2, triclinic, Z = 2, a = 6.141(2) Å, b = 7.213(1)Å, c = 22.219(5)Å, a = 84.60(2)°, b = 88.81(2)°, g = 89.98(2)°. There are two independent molecules in the unit cell, neither of which is planar. The molecules pack with a somewhat unusual pattern with the aromatic rings of adjacent molecules oriented about half-way between the expected face-to-face or edge-to-face arrangements.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2536-2539

 

Synthetic, spectroscopic and biocidal aspects of sixteen to twenty two membered tetraazamacrocyclic complexes of tin(II)

Ashu Chaudhary , R V Singh & Anita Phor*

 

The template condensation of malonic, succinic, glutaric, adipic or phthalic acid with 1,3-phenylenediamine in the presence of tin(II) chloride resulted in the isolation of macrocyclic complexes of the type [Sn(N4macn)Cl2]. These complexes have been characterized by chemical analysis, IR, 1H NMR and 119Sn NMR spectral studies, X-ray powder diffraction, molecular weight determinations and conductivity measurements. An octahedral geometry around the tin atom is suggested for [Sn(N4macn)Cl2] complexes. The biological activities of all the complexes have been studied by screening them against organisms E. coli,S. aureus, F. oxysporum and A. alternata and the results have been compared.

 

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2540-2543

 

Synthesis and spectroscopic characterization of molybdenum(0) and molybdenum(II) carbonyl benzophenoneazine complexes

 

M A Affan*, Ramli bin Hitam & Mustaffa bin Shamsuddin

 

A chelating 2-methylpyridylbenzophenoneazine ligand has been prepared by the condensation of 2-acetylpyridine with benzophenone hydrazone. Reaction of the ligand with Mo(CO)6 gives 12-methylpyridylbenzophenoneazine)tetracarbonylmolyb-denum(0) complex where the ligand is bidentate N, N. Oxidative-addition of the tetracarbonyl complex with 1 mol equivalent of bromine, yields the neutral seven-coordinated dibromotri-carbonylmolybdenum(II) azine complex. Treatment of the tetracarbonyl complex with 1 mol equivalent of PPh3 gives the expected tri-carbnonylmolybdenum(0)-azine triphenylphosphine substituted complex.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2544-2547

 

Synthesis and characterization of lanthanide complexes of 1-phenyl-3-methyl-5-hydroxy-4-pyrazolyl-phenyl ketone-2′-picolinoyl hydrazone

B T Thaker *& Chetan K Modi

 

The ligand, 1-phenyl-3-methyl-5-hydroxy-4-pyrazolyl phenyl ketone 2′-picolinoyl hydrazone (HL) is prepared by condensation of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone with 2-picolinic acid hydrazide. Seven complexes of lanthanides with HL of the type [Ln(HL)3].2H2O (where Ln=trivalent lanthanides such as La, Ce, Nd, Sm, Gd, Dy and Er) have been synthesized and characterized by complexometric titration of lanthanoid ions, elemental analysis, molar conductance, IR, 1HNMR, electronic spectral studies and TGA analysis. IR spectra and thermogram shows the presence of two water moieties outside the coordination sphere and are non-electrolytic in nature. The complexes appear to be nine-coordinated and ligand act as a tridentate ligand.

 

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2548-2550

 

 

Trace level determination of bromide in presence of large concentration chloride by differential pulse polarography

P Sharma* & Rakesh Sharma

The optimum conditions for the determination of bromide at low concentrations has been developed employing differential pulse polarography. A detection limit of 0.3 µg/ml has been achieved. The method has been successfully applied for the analysis of bromide content in underground waters and food products.

Indian Journal of Chemistry
Vol. 41A, December 2002, pp 2551-2554

 

Adsorption of oxine and its derivatives on granular activated carbon

Ms Veena Mustoor & G S Natarajan*

 

The adsorption of 8-hydroxyquinoline and some of its derivatives on granular activated carbon, F-400 sample, has been studied. The adsorption isotherms have been determined and tested for adherance to Freundlich and Langmuir theories. The surface area calculated on the basis of monolayer formation of these adsorbates has been correlated with structure of the oxines.