Indian Journal of Chemistry

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

 

VOLUME 42A

NUMBER 2

FEBRUARY 2003

 

CONTENTS

Advances in Contemporary Research

 

Saccharide complexes of lanthanides

Chebrolu P Rao* & T Mohan Das

227

Papers

 

Theoretical designing of copolymers of donor-acceptor polymers based on polysilole

Geetika Gandhi & A K Bakhshi*

240

Copper containing mixed oxides for catalytic oxidation of toluene and phenol in  solid-liquid phase

 C Srinivasan & B Viswanathan*

250

A novel magnetic exchange mechanism in bridged copper(II) coordinations of  naturally occurring spin carriers, viz., ortho-functionalized p-   naphthoquinones

 Sandhya Rane*, Sunita Gawali, Subhash Padhye, Sadgopal Date & Pramod    Bakare

255

Synthesis and substitution reactions on dicholoro[2-(N-(2-hydroxyphenyl)- carbamoyl)-pyridine]bis(dimethyl sulphoxide)-ruthenium(II)

Sujit Dutta & Pabitra K Bhattacharya*

262

Biocidal and antifertility activities of organotitanium and organozirconium complexes derived from nitrogen and sulphur/oxygen donor ligands

Saurabh  Saurabh Dave, Ashu Chaudhary, Mithilesh Agarwal, S C Joshi &
R V Sing  R V Singh* Mithlesh

268

Chemical speciation and biological activity of bivalent metal complexes of   polydentate amide ligands

Bhagwan Singh Garg*, Meenu Sarbhai & Deo Nandan Kumar

275

 

Synthesis and characterization of manganese(II), cobalt(II), nickel(II), copper(II),  zinc(II), cadmium(II), iron(III), zirconium(IV), dioxo- molybdenum(VI) and dioxouranium(VI) coordination compounds of polystyrene-supported tridentate dibasic Schiff base derived from semicarbazide and 3-  formylsalicylic acid

D Kumar*, A Syamal & A K Singh

280

Multiple interactions in Zn(II) ternary systems of phenanthroline bridging polyaza  ligand and adenosine, 5¢-triphosphate

Yanhe Guo, Qingchun Ge, Hai Lin, Huakuan Lin* & Shourong Zhu

287

Notes

 

Thermodynamics of ternary mixtures: Excess isentropic compressibilities

V K Sharma*, K C Kalra, Romi & Ashma Katoch

292

A study of the electrochemical absorption and diffusion of hydrogen into mercury in acidic solution

 M  Jafarian*, M G Mahjani, O Azizi & F Gobal

295

Surface properties and catalytic activity of phosphate modified zirconia

V K Smitha, H Suja, Joyce Jacob & S Sugunan*

300

Studies on the reactions of lanthanide trichloride isopropanol complex,  LnCl3.3PriOH, with Nb(OPri)5 or Al(OPri)3

Shashank Mishra & Anirudh Singh*

305

Thiosemicarbazonates of silver(I) : synthesis, spectroscopy and reactivity towards             triphenylphosphine

 Tarlok S Lobana*, Gaurav Bhargava , Vinay Sharma & Manoj Kumar*

309

Synthesis, antitumor and antibacterial activity of some Ru(bpy)2+2/4-substituted  thiosemi-carbazide complexes

U K Mazumder*, Malaya Gupta, A Bera, S Bhattacharya, S Karki, L Manikandan & S Patra

313

Synthesis and crystal structure of schiff base pyrazolone

 Miao Ru, Li Shuoliang, Yang Rudong, Yan Lan* & Yuan Wenbing

318

Synthesis and characterization of Cr(III), Mn(III), Fe(III), Ti(III),VO(IV), Th(IV), Zr(IV) and UO2(VI) polychelates derived from bis-bidentate salicylaldimine  Schiff base

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

322

One-dimensional chain crown ether complexes. Synthesis and crystal structure of  [Na(18-crown-6)] 2[M(mnt)2](M = Zn, Cd)

Qingjiang Yu, Jianmin Dou*, Dacheng Li, Daqi Wang, Baoyun Zhong,   Yong Wei & Peiju Zheng

327

 

A rapid spectrophotometric method for the determination of trichloromethane   sulphenyl chloride derivatives and commercial fungicides

 D K Sharma*, Sumita Sood, Ramesh Kumar & B C Verma

331

 

 


Indian Journal of Chemistry

Vol. 42A, February 2003, pp 227- 239

 

 

Saccharide complexes of lanthanides

Chebrolu P Rao* & T Mohan Das

 

The main focus of this review article is to bring out different aspects of interactions of saccharides with lanthanide ions. Various characteristic properties of lanthanide-saccharide complexes have been compared appropriately with those of the transition metal ones

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 240-259

 

 

Theoretical designing of copolymers of donor-acceptor polymers based on polysilole

Geetika Gandhi & A K Bakhshi *

 

The electronic structures and conduction properties of quasi-one-dimensional superlattices (copolymers) (AmBn)x of two silole based donor- acceptor polymers PSICO (A)x and PSICN (B)x calculated on the basis of the negative factor counting method in the tight-binding approximation are reported. The repeat unit of PSICO and PSICN consists of bicyclopentadisilole unit bridged by an electron-accepting group in PSICO and C(CN)2 in PSICN). The copolymers, on the basis of the band positions of PSICO and PSICN, are found to belong to the class of type-II staggered superlattices. The trends in the electronic properties of the copolymers as a function of (i) the block size m of A, (ii) the block size n of B, (iii) the block sizes m and n keeping m/n constant and (iv) the arrangement of units in the copolymer chain (periodic or aperiodic) are discussed.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 250-254

 

 

Copper containing mixed oxides for catalytic oxidation of toluene and phenol in solid-liquid phase

C Srinivasan & B Viswanathan*

 

The YBa2Cu3O7- and its precursors (Y2Cu2O5 and BaCuO2) have been used as a catalyst for toluene and phenol oxidation in solid- liquid phase. It has been observed that the oxide without Cu(III) content and without alkaline earth metal,Y2Cu2O5 have low activity for the decomposition of H2O2 and high activity for these oxidation reactions. Maximum toluene conversion (25.9%) has been observed when acetonitrile is used as a solvent and maximum phenol conversion (45.3%) when water is used as a solvent. Mechanism of toluene oxidation on these mixed oxides has been suggested.

 

 

 

Indian Journal of Chemistry Vol.

42A, February 2003, pp 255-261

 

 

A novel magnetic exchange mechanism in bridged copper (II) coordinations of naturally occurring spin carriers viz. ortho-functionalized p-naphthoquinones

Sandhya Rane, Sunita Gawali , Subhash Padhye, Sadgopal Date & Pramod Bakare

 

Magnetic exchange and charge transfer mechanisms in dimeric (1) [Cu(Lw)2H2O]2 and monomeric (2), [Cu(phth)2] complexes of lawsone (2-hydroxy-1,4-naphthoquinone) and phthiocol (3-methyl-2-hydroxy 1,4-naphthoquinone) are described. Magnetic susceptibility measurements of (1) are fitted to Heisenberg’s isotropic spin pair (S’ = 1,1) model and tetranuclear (S’ = ½, ½, ½, ½) spins in a two dimensional model. Both models result in intradimer antiferromagnetic coupling (J = 44.4 cm1) between [Cu(NSQ)]2 units and ferromagnetic coupling (zJ1 = 28.5 cm1) between one Cu(II)NSQ coordinated unit (where NSQ = naphtho-semiquinone).

 

Latter interaction leads to a triplet ground state and triplet-triplet intradimer interaction governs the “quintet state” at room temperature, as detected from X- and Q-band EPR studies. The zero-field split interaction (0.024 cm1) exhibits contributions from Dpd (0.071 cm1) and combined Dd and Danti (+0.095 cm1) interactions. The intradimer exchange is due to a stacked (S’ = 1,1) spin pair with r = 3.04 Å. The monomeric complex (2) is devoid of such interactions due to the bulky methyl group at C3 position of quinonoid ring.

 

Cyclic voltammograms of (1) and (2) show an anodic peak at +0.22 V, assigned to Cu(0))  Cu(II )charge transfer. Only one redox couple at E1/2 = 0.687 V due to NSQ  CAT (catechol) charge transfer leads to radical coordination in (1). However quasireversible NQ NSQ redox couple at E1/2 = 0.525 V together with an irreversible NSQ  CAT reduction peak in (2) at E1/2 = 0.75 V indicate fully the presence of oxidized (NQ) i.e. naphthoquinone ligation in (2).

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 262-267

 

 

Synthesis and substitution reactions on
dicholoro[2-(N-(2-hydroxyphenyl)-carbamoyl)pyridine]bis
(dimethyl sulphoxide)-ruthenium(II)

Sujit Dutta & Pabitra K Bhattacharya*

 

The amide ligand 2-(N-(2-hydroxyphenyl)carbamoyl)pyridine (H2L1) has been prepared by condensing pyridine-2-carboxylic acid with 2–aminophenol. This amide ligand has been characterised by elemental analysis, infrared, 1H NMR and mass spectral studies. The complex [Ru(H2L1)(dmso)2Cl2] I, has been synthesised by the reaction of [Ru(dmso)4Cl2] with H2L1. Further reaction of I with -acidic diimines, 2,2'-bipyridine and 1,10-phenanthroline, lead to the substitution of the coordinated dmso molecules in I forming heteroleptic ruthenium complexes [Ru(bpy)(HL1)Cl2], II and [Ru(phen)(HL1)Cl2], III (bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline), respectively. The complex I is diamagnetic while the complexes II and III are paramagnetic due to one electron and show rhombic EPR spectra at 77K. All the complexes show intense absorptions due to metal to ligand charge transfer (MLCT) transitions in the electronic spectra. The IR and 1H NMR spectral studies indicate that in I, the amide ligands coordinate to the ruthenium (II) ion as a bidentate ligand, coordinating from pyridyl nitrogen and the carbonyl oxygen of the amide linkage, leaving the other potential coordinating phenolic functional group intact. The IR spectral studies indicate that in II and III, the amide ligand coordinates from the pyridyl nitrogen and the amidato nitrogen, leaving the other potential coordinating phenolic functional group intact. The complex I undergoes a reversible ruthenium(II)/ruthenium(III) oxidation at –0.17 V in acetonitrile solution, while the complexes II and III undergo irreversible ruthenium(III)/ruthenium(IV) oxidation at ca. 0.37 V.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 268-274

 

 

Biocidal and antifertility activities of organotitanium and organozirconium complexes derived from nitrogen and sulphur/oxygen donor ligands

Saurabh Dave, Ashu Chaudhary, Mithlesh Agawal, S C Joshi & R V Singh*

 

A new class of unsymmetrical organotitanium(IV) and organozirconium(IV) complexes of biologically potent ligands derived from heterocyclic ketones and semicarbazide hydrochloride/ thiosemicarbazide have been prepared and characterized on the basis of IR and 1H NMR spectral studies and elemental analysis, conductance measurement and molecular weight determinations. The ligands act as monobasic bidentate with N OH and N SH as donor systems. All the organotitanium(IV) and organozirconium(IV) complexes and their parent ligands have been screened against a number of microbes and their sterilizing power on male rat has been tested and discussed with positive findings.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 275-279

 

 

Chemical speciation and biological activity of bivalent metal complexes of polydentate amide ligands

Bhagwan Singh Garg*, Meenu Sarbhai & Deo Nandan Kumar

 

 

Stability constants of N,N-bis-(3-carboxy-1-oxopropanyl)-1,2-ethylenediamine(L1), N,N-bis-(3-carboxy-1-oxopropanyl)-1,2-phenylenediamine(L2), N,N-bis-(2-carboxy-1-oxophenelenyl)-1,2-phenylenediamine(L3) have been determined in aqueous medium (for L1 & L2) and 75% (v/v) methanol-water medium for L3 pH-metrically. The formation constants (logn) have been calculated using the Bjerrum half integral method and weighted least squares method. Species distribution curves of complexes have been plotted as a function of pH which shows at lower pH values 1:1 complexes are formed and 1:2 complexes are formed at neutral or higher pH. The biological study indicates that ligands and their complexes are better fungicidal than bactericidal. Copper complexes of all the ligands showed potential antifungal and antibacterial activities. Ligand L3 and its copper(II) complexes are most effective against A. niger, E. coli and S. aureus

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 280-286

 

Synthesis and characterization of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), iron(III), zirconium(IV),
dioxo- molybdenum(VI) and dioxouranium(VI) coordination compounds of polystyrene-supported tridentate dibasic
Schiff base derived from semicarbazide and 3-formylsalicylic acid

D Kumar*, A Syamal & A K Singh

 

Several new polystyrene-supported metal coordination compounds of the types: PS-LMDMF (where M = Cu, Zn, Cd, MoO2, UO2), PS-LFeCl2DMF, PS-LZr(OH)22DMF and PS-LM3DMF(where M = Mn, Co, Ni) have been synthesized by the reaction of polystyrene-anchored Schiff base(PS-LH2)(obtained by the reaction of chloromethylated polystyrene, semicarbazide and 3-formylsalicylic acid) with metal ions. The compounds have been characterized by elemental analysis, IR, reflectance, ESR spectral and magnetic susceptibility measurements. The shifts of the (C=N)(azomethine), (C–O) (phenolic) and (C–O)(enolic) stretches of PS-LH2 upon complexation indicate the tridentate (ONO donor) behaviour of PS-LH2. The Mn(II), Co(II), Ni(II), Cu(II) and Fe(III) compounds are paramagnetic while others are diamagnetic. PS-LCuDMF is square planar, PS–LMDMF (M = Zn, Cd) is tetrahedral, PS-LMO2DMF (M=Mo,U),PS-LM3DMF (M = Mn, Co, Ni) and PS–LFeCl2DMF are octahedral, while PS-LZr(OH)22DMF is pentagonal bipyramidal. The ESR and magnetic measurements data indicate the magnetically dilute nature of the metal centres.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 287-291

 

 

Multiple interactions in Zn(II) ternary systems of phenanthroline bridging polyaza ligand and adenosine, 5’-triphosphate

Yanhe Guoa, Qingchun Gea, Hai Linb, Huakuan Lina* & Shourong Zhua

 

The stability of Zn(II) ternary complexes of phenanthroline bridging polyaza ligand and ATP have been determined using potentiometric pH titrations, 1H and 31P NMR spectra. Protonated metal complexes interact with the polyphosphate chain of the nucleotide substrate by coordination, electrostatic and H-bonding interactions, as well as stacking interactions between the phenanthroline moiety of L and the nucleoside residue of ATP. Moreover, ion--donor, hydrophobic and even van der Waals interactions may exist in the ternary systems. The recognition of nucleotides is promoted by adding Zn(II) to the receptor/ substrate system. Zn(II) acts as a “messenger” to bridge the polyamine and ATP, which in turn leads to the competition between the mixed ligands in binding zinc ion. Thus, the supramolecules formed by self-assembly are good models to mimic the active center of the ATPase.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 292-294

 

 

Thermodynamics of ternary mixtures : Excess isentropic compressibilities

V K Sharma*, K.C. Kalra, Romi & Ashma Katoch

 

Ultrasonic velocity data for nitrobenzene(i) + benzene(j) + toluene, or + o-xylene, or + p-xylene (k) ternary mixtures have been determined as a function of composition at 298.15K. The observed data have been utilized to evaluate excess isentroic compressibilities, . values have also been computed using Flory theory. It has been observed that values evaluated from Flory theory make qualitative agreement with the values evaluated from experimental data.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 295-299

 

 

A study of the electrochemical absorption and diffusion of hydrogen into mercury in acidic solution

M Jafarian, M G Mahjani, O Azizi & F Gobal

 

The electrochemical adsorption and diffusion (dissolution) of hydrogen into mercury have been studied by the methods of cyclic voltammetry and impedance spectroscopy. In the potential range of -0.15 to -1.5 V (vs. Ag/AgCl) two peaks at -0.4 and -0.8 V have been observed and are associated with the adsorption and absorption of hydrogen. Impedance studies exhibited two overlapping semi-circles terminating in a straight line in the low potential region. The size of the semi-circles increase as the potential is raised and attributed to the increased resistive effect of the dissolved hydrogen. The value of the real component upon increasing the measurement potential to -0.9 V is followed by a sharp decrease at higher potential and indicates the removal of the absorbed as well as adsorbed hydrogen atoms through the HER routes.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 300-304

 

 

Surface properties and catalytic activity of phosphate modified zirconia

Smitha V K, Suja H, Joyce Jacob & S Sugunan*

 

Preparation and physico-chemical characterisation of phosphate modified zirconia systems and their application to Friedel Crafts benzylation and benzoylation of toluene havw been reported. The influence of transition metals on the surface properties and catalytic activity has also been discussed.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 305-306

 

 

Studies on the reactions of lanthanide trichloride isopropanol complex, LnCl3.3PriOH, with Nb(OPri)5 or Al(OPri)3

Shashank Mishra & Anirudh Singh*

 

Reactions of LnCl3.3PriOH (Ln = Y, La, Pr, Nd, Sm, Gd, Er) with three equivalents of Nb(OPri)5 or freshly distilled Al(OPri)3 yield quantitatively derivatives of composition Ln{Nb(OPri)5Cl}3 or Ln{Al(OPri)3Cl}3, respectively. All these novel derivatives have been characterized by elemental analysis and spectroscopic (IR, 1H, 13C and 27Al NMR) studies. Molecular weight measurements have also been carried out on niobium derivatives.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 309-312

 

 

Thiosemicarbazonates of silver(I) : synthesis, spectroscopy and reactivity towards triphenylphosphine

Tarlok S.Lobana*, Gaurav Bhargava , Vinay Sharma & Manoj Kumar*

 

The new tripodal ligand tris-[{2-benzaldehyde}-oxoethyl}amine]-thiosemicarbazone, N[CH2-CH2-O-{o-C6H4-CH=N- NH-C(=S)-NH2}]3 (abbreviated as H3L) on reaction with silver(I) acetate in 3:1 (M:L) mole ratio in ethanol formed {Ag5L(OAc)2} (1), which in presence of excess triphenylphosphine (PPh3) in chloroform–ethanol mixture yielded, {Ag5L(OAc)2(PPh3)12}(2) ( L is deprotonated) . Similarly reactions of silver(I) acetate with salicylaldehyde thiosemicarbazone (H2stsc), furan-2-carbaldehyde thiosemicarbazone (Hftsc) and pyrrole-2-carbaldehyde thiosemicarbazone (Hptsc) in presence of PPh3 in ethanol-chloroform formed [AgL(PPh3)n] complexes (3-5)[L (n) = Hstsc (1); ftsc (3); ptsc (4) ; thiosemicarbazones are monodeprotonated]. The complexes (1-5) have been characterised by their physical properties, analytical data , IR and UV spectroscopic studies.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 313-317

 

 

Synthesis, antitumor and antibacterial activity of some Ru(bpy)2+2/4-substituted thiosemicarbazide complexes

U K Mazumder*, Malaya Gupta, A Bera, S Bhattacharya, S Karki, L Manikandan & S Patra

 

Complexes of N-substituted thiosemicarbazides with Ru(II)-2,2 bipyridyl have been prepared and characterised by IR, 1H NMR and UV/Vis spectroscopy in addition to their elemental analysis. Based on molecular mechanics simulations using HyperChem®, the complexes are designed for anticancer activity against Ehrlisch Ascites Carcinoma. Their effects on the hematological profile of the tumor hosts have also been studied. The complexes are found to possess prominent antibacterial activity.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 318-321

 

 

Synthesis and crystal structure of schiff base pyrazolone

Miao Ru, Li Shuoliang, Yang Rudong, Yan Lan* &Yuan Wenbing

 

Tris[2-(((1-phenyl-3-methyl-5-pyrazolone-4)methylidene)amino)ethyl]amine Schiff base pyrazolone [III], has been prepared in high yield via vinamidmium salt. The crystal structure of [III] is discussed.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 322-326

 

 

Synthesis and characterization of Cr(III), Mn(III), Fe(III), Ti(III),VO(IV), Th(IV), Zr(IV) and UO2(VI) polychelates derived from bis-bidentate salicylaldimine Schiff base

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

 

The polychelates of Cr(III), Mn(III), Fe(III), Ti(III), VO(IV), Th(IV), Zr(IV) and UO2(VI) with 4,4-bis[(N-p-nitrophenylsalicylaldimine-5)-azo]biphenyl (BNSAB) have been synthesised and characterized by elemental analysis, magnetic susceptibility, electronic and IR spectral data and thermogravimetric analysis. The ligand BNSAB acts as bis-bidentate ONNO donor. The thermal data have been analyzed for the kinetic parameters by Broido’s method. The electrical conductivity of the ligand and polychelates has been measured which indicate their semiconducting behavior in the studied temperature range. The ligand and its polychelates have also been screened for their antimicrobial activity using various microorganisms.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 327-330

 

 

One-dimensional chain crown ether complexes. Synthesis and crystal structure of [Na(18-crown-6)]2[M(mnt)2](M = Zn, Cd)

Qingjiang Yu, Jianmin Dou* , Dacheng Li, Daqi Wang, Baoyun Zhong Yong Wei & Peiju Zheng

 

The reactions of 18-crown-6 with Na2[Zn(mnt)2] and Na2[Cd(mnt)2] have been studied and the complexes [Na(18-C-6)]2[M(mnt)2](M = Zn, Cd)are characterized by elemental analysis, IR spectrum and X-ray diffraction analysis. 1 and 2 belong to monoclinic, space group c2/c with cell dimensions, 1 : a = 2.2418(6),b = 1.1359(3),c = 1.9887(6)nm, β= 120.391(4), V = 4.368(2)nm3,Z = 4,Dcalcd = 1.399 Mg/m3,F(000) = 1920, R1 = 0.0362,wR2 = 0.0560 and 2: a = 2.2547(6),b = 1.1412(3),c = 1.9938(6)nm,β=119.715(4), V = 4.455 nm3,Z = 4,Dcalcd = 1.442 Mg/m3,F(000)= 1992,R1 = 0.0384,wR2 = 0.0575. Two complexes display a one-dimensional chain of [Na(18C6)]+ complex cations and [M(mnt)2] 2- (M = Zn, Cd) complex anion bridged by Na-O interactions between adjacent [Na(18C6)]+ units respectively.

 

 

 

Indian Journal of Chemistry

Vol. 42A, February 2003, pp 331-332

 

 

A rapid spectrophotometric method for the determination of trichloromethane sulphenyl chloride derivatives and
commercial fungicides

D K Sharma*, Sumita Sood, Ramesh Kumar & B C Verma

 

A new, simple and rapid spectrophotometric method for the microdetermination of trichloromethane sulphenyl chloride derivatives (RSCCl3) based on their reaction with thiophenol in acetonitrile in the presence of triethylamine is described. The yellow colour, which develops instantaneously on mixing the reagents in acetonitrile, is stable for atleast 6 h and is measured at 450 nm. Beer’s law is applicable upto 200 µg ml-1 of each derivative concentration. The method has been successfully adapted to the analysis of captan and folpet fungicides based on these derivatives in their commercial formulations for the purpose of quality control.