Indian Journal of Chemistry
Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical
VOLUME 41A
NUMBER 7
JULY 2002
CONTENTS
Papers
1329
Ab-initio molecular orbital calculations on
group III elements and their halides
R Amrutha, L Sangeetha, Deepak
Samuel & P Chandran*
1334
Prediction of chiral separation of ketoprofen
using experimental design
K Valliappan*, K Kannan, R Manavalan &
C Muralidharan
1341
Multiple substituent effects on 13C chemical
shifts in phenylstyryl ketones: Applicability of
interactive free energy relationship
The effect of halogenation of dimeric hydrides of boron,
aluminium and gallium is studied theoretically. The total
energy, ionization potential, charge density and
dipolemoments are calculated and it is found that
subtitution by bromine decreases the ionization potential
and introduction of halogen atoms alters the entire charge
distribution.
The paper demonstrates how experimental design could be
applied to predict chiral resolution and run time for indirect
chiral high performance liquid chromatography (HPLC)
analysis of ketoprofen. An attempt is made to establish
quantitative
relationship
between
chromatographic
variables and the response factors
Cross-interaction constants have been calculated using
13C NMR chemical shifts for 23 mono- and di- substituted
phenylstyryl ketones.
S R Annapoorna, M Prasad Rao &
B Sethuram*
1346
Synthesis and electronic spectral
characterization of conducting
benzidine copolymers
M Muruganandham & M Swaminathan*
1349
Vapour phase oxidation of benzyl alcohol on
A2BO4 type perovskite related oxide
C Srinivasan & B Viswanathan*
The benzidine copolymers, benzidine-aniline, benzidineortho anisidine and benzidine-para anisidine have been
synthesized and their conductivities and electronic spectra
analyzed. The copolymers are found to have conductivities
in the range of semiconductors.
1355
Surface acidity and catalytic activity of mixed
Fe-Al and Cr-Al pillared montmorillonites
S Sugunan* & K S Rahna
1363
Incorporation of iron and chromium oxide pillars along
with Al2O3 pillars within the interlayers of a
montmorillonite clay has been investigated. Incorporation
of Fe and Cr has changed the properties of Al pillared
montmorillonite. Fe pillared systems have been found to be
very good catalysts for benzoylation reaction.
Synthesis and crystal structure of two
extensively hydrogen bonded
network of Cu(II)
Sudipta Dalai, Partha Sarathi
Mukherjee, Steven Geib &
Nirmalendu Ray Chaudhuri*
1369
Electron spin resonance, magnetic and
superoxide dismutase activity of binuclear
imidazolate bridged complexes
R N Patel*, K K Shukla, N Singh &
K B Pandeya
1374
Electron paramagnetic resonance, magnetic susceptibility
and superoxide dismutase activity measurements of
imidazolate
bridged
[(Salval)Cu-Im-Cu(Salval)]Na,
[(Salval)Cu-Im-Ni(Salval)]Na
and
[(Salval)Cu-ImZn(Salval)]Na
complexes,
[where
salval
=
salicyledenevalinate, im = imidazolate ion,] are described.
Isomeric mixed dioxolene 2-(arylazo)pyridine
complexes of osmium(II): Synthesis, spectra
and electrochemistry
Doyel Bose, Hafijur Rahaman, Jaya Banerjee,
Naba Kumar Mondal &
Barindra Kumar Ghosh*
1380
Synthesis and reactivity of the copper (II)
complexes of N--acetophenyl-Xsalicylaldimines (  = 4 or 3, X = H, 5-Br or
3-COOH ). Molecular structure of bis-( N-4acetophenyl- salicylaldiminato) copper(II)
Rajib Lal De , Indrajit Banerjee ,
Subhadra Guha & Alok K Mukherjee
1385
Synthesis and characterization of a chelating
resin containing ONO donor tridentate Schiff
base and its coordination compounds with
copper(II), nickel(II), cobalt(II), iron(III),
zinc(II), cadmium(II), manganese(II), molybdenum(VI), zirconium(IV) and uranium(VI)
A Syamal, D Kumar*, A K Singh, P K Gupta,
Jaipal & L K Sharma
Polystyrene supported tridentate dibasic Schiff base
(PS-LH2) reacts with metal salts/coordination compounds to
form compounds of the type PS-LM.xDMF, PS-LFeCl
2DMF and PS-LZr(OH)2.2DMF.
1391
Host-guest chromatographic behaviour of
ketones in micellar paper chromatographic
separation
Zhengsheng Fu*, Guoqin Lia , Aimei Yang,
Weidong Liang & Zhiguo Wang
Separation of 14 ketone compounds by paper
chromatography using pure water micellar solution of
hexadecyltrimethyl ammonium bromide and/or sodium
dodecylsulphate as the mobile phase has been reported.
Suitability between the solute molecules (guest) and
micelles (host) is the main driving force of chromatographic
migration.
Notes
1397
Immobilization of dithiooxamide in
biopolymer and synthetic films for possible use
in optical fibre copper probe
Dithiooxamide has been immobilized in a biopolymer
matrix for the quantitative determination of Cu (II) by an
optical fibre method. Immobilization of dithiooxamide in
poly(methyl)methacrylate alone shows characteristics
comparable to that of the biopolymer matrix .
Anupa Murugkar, Meena Karve, Subhash
Padhye*& R Narayanaswamy
1402
Organization of amphiphiles, Part-II—Surface
activity of polyoxyethylated alkyl phenols at
air-water interface
Lingaraj Sahoo, Pramila K Misra*
& P Somasundaran
1406
Olefin epoxidation catalyzed by novel
nickel(II)-complexes containing tridentate
Schiff-base ligands
Debabrata Chatterjee* &
Sanghamitra Mukherjee
1410
Kinetics of dissociation of tris – (2, 2–
bipyridyl) and tris – (1, 10 – phenanthroline)
iron (II) complexes in the presence of OH– in
the water pools of CTAB reverse micelles
G Venkateswarlu, P Syamala, P V Subba Rao*
& K Ramakrishna
1415
Synthesis and crystal structure of twodimensional network DB18-C-6 complex:
[Na(DB18-C-6)]2[Pt(SCN)6]
Tong Wanga,b, Jianmin Dou* a, Dacheng Lia,
Daqi Wanga, Meimei Wua & Peiju Zhengc
1417
Studies on cerium(III) complexes of piperidin4-ones
Kuppusamy Selvaraj* &
Chinniagounder Theivarasu
Kinetics of dissociation of tris (2, 2-bipyridyl) and tris
(1, 10 –phenanthroline) complexes in the presence of OH–
ion in the water pools of CTAB reverse micelles in hexanechloroform mixtures has been studied. Increase in rate due
to decrease in ionic strength predominates over the effect of
increase in dielectric constant with increase in W.
1421
Synthesis and characterization of
acetylferrocenyl thiosemicarbazone derivatives
of dichlorobis(cyclopentadienyl)hafnium(IV)
Soumitra Kumar Sengupta*, Om Prakash
Pandey, Alpana Bhatt, Vinita Srivastava &
Kushal Nath Mishra
1424
Synthesis and physico-chemical studies of
manganese(II), nickel(II), cobalt(II), copper(II)
and zinc(II) complexes of new 13-membered
pentaazamacrocycles with N4 donor sets
Tahir Ali Khan*, Manzoor A Rather,
Ajax K Mohamed, Khan S. Islam &
Nafees Jahan
1428
Stability
studies
on
12-(5’-8’-hydroxyquinolinic)methylene-1,4,7,10-tetraazacyclo
tridecane-11,13-dione,
5-substituted 1,10phenanthroline-copper(II) with Cu2+ or Co2+
binuclear mixed-coordinated systems
Xiaojun Zhao, Xuncheng Sua, Encui
Yang, Huakuan Lin*, Shourong Zhu,
Hongwei Sun & Yunti Chen
1433
Determination of zinc in high purity gallium
by differential pulse anodic stripping
voltammetry
A sensitive differential pulse anodic stripping voltammetric
method is proposed for the determination of zinc in high
purity gallium.
Suvarna Sounderajan, Avanti Singh &
M M Palrecha*
1436
Spectrophotometric determination of iron in
traces amount using 5-bromo-salicylaldehyde
thiosemicarbazone
A simple, sensitive and specific spectrophotometric method
has been developed for the determination of iron(II) in
aqueous dimethylformamide. The method has been
employed successfully for the determination of Fe(II) in
grape leaves, multivitamin capsules and human blood.
G Ramanjaneyulu, P Raveendra Reddy*,
V Krishna Reddy & T Sreenivasulu Reddy
1438
Bismuth selective antimony(III) silicate
inorganic ion–exchanger
Antimony(III) silicate has been synthesised, characterised,
and its ion exchange properties have been ascertained.
Binary separations of Bi(III) from Pb(II), Cu(II), Zn(II) and
Hg(II) have been achieved from a column of the exchanger.
C Reetha, K K Aravindakshan &
C Janardanan*
.
Authors for correspondence are indicated by (*)
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1329-1333
Ab-initio molecular orbital calculations on group III
elements and their halides
R Amrutha, L Sangeetha, Deepak Samuel & P Chandran*
The effect of halogenation of dimeric hydrides of boron, aluminium and gallium is studied
theoretically for the first time. Ab-initio molecular orbital theory at the RHF/6-31G* level has been used
to investigate the physico-chemical properties of the dimers of hexahydrides and halogen substituted
hexahydrides. The total energy, ionization potential, charge density and dipole moments are calculated.
Halogenation of the dimeric hydrides of Group IIIA elements brings out some interesting properties of the
electronic structure of these molecules. From the calculation of ionization potential, it is seen that
substitution by bromine decreases the ionization potential. The calculation also shows that whenever
substitution of halogen occurs at the bridge position, the ionization potential is further lowered. From the
charge density calculation, it is observed that the introduction of halogen (F, Cl or Br) atoms alters the
entire charge distribution. Aluminium halides have stable structures and charge distribution compared to
other halides of Group III elements. If the bridge atoms are not halogenated gallium behaves more or less
like aluminium in all respects. A possibility of existence of dimers of gallium halides is explored. The
dipole moments of the molecules are calculated and reported.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1334-1340
Prediction of chiral separation of ketoprofen using
experimental design
K Valliappan*, K Kannan, R Manavalan & C Muralidharan
The paper demonstrates how experimental design could be applied to predict chiral resolution and run
time for indirect chiral high performance liquid chromatography (HPLC) analysis of ketoprofen. An
attempt is made to establish quantitative relationship between chromatographic variables and the response
factors (resolution and retention time). The effects of important chromatographic variables on chiral
resolution and retention time have been highlighted by way of interaction studies. This technique enables
optimal utilization of resources by avoiding trial and error approach. The study advocates that
experimental design is a prospective tool to predict and optimize chromatographic conditions for chiral
HPLC analysis.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1341-1345
Multiple substituent effects on 13C chemical shifts in
phenylstyryl ketones: Applicability of interactive free
energy relationship.
S R Annapoorna, M Prasad Rao & B Sethuram*
13C chemical shifts for 23 mono- and di-substituted phenyl styryl ketones have been determined. The
shieldings and deshieldings are compared with previous results for other aromatic derivatives.
Correlations of the 13C chemical shifts of vinyl carbons with Hammett  parameters was determined to
provide a consistent picture of electronic effects transmitted through the carbon framework of the
compounds studied. Slopes obtained from such Hammett's plots were termed as , and using these ''
values applicability of interactive free energy relationship to chemical shift values has been tested. The
cross- interaction constants qx and qy values for C- were found to be -1.02 and -1.20 and for C- are 1.46 and -1.19.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1346-1348
Synthesis and electronic spectral characterization of
conducting
benzidine copolymers
M Muruganandham & M Swaminathan*
The copolymers benzidine-aniline, benzidine-o-anisidine and benzidine-p-anisidine have been
synthesised by chemical method. Their absorption and fluorescence spectra have been analysed. The
copolymers are found to have conductivities in the range of semiconductors. In copolymers the longer
wavelength absorption band of homopolymer is extended to infrared region.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1349-1354
Vapour phase oxidation of benzyl alcohol on A2BO4 type
perovskite related oxide
C Srinivasan & B Viswanathan*
The substitution of strontium at lanthanum site in the sublattice of La2CuO4 results in the formation
of Cu3+ species and formation of defects in the oxygen sublattice. As the strontium content increases the
oxygen non-stoichiometry increases, whereas Cu3+ content attains maximum at x = 0.3. As the oxygen
non-stoichiometry () increases, the selectivity towards toluene increases, thus showing that formation of
toluene depends on the oxygen non-stoichiometry. When the reaction is carried out in nitrogen
atmosphere the LaCuO4 system shows good selectivity towards toluene indicating the dependence of
toluene selectivity on the atmosphere in which the reaction is carried out.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1355-1362
Surface acidity and catalytic activity of mixed Fe-Al and
Cr-Al pillared montmorillonites
S Sugunan* & K S Rahna
The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3 pillars
within the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated
for the first time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared
with those obtained by temperature programmed desorption of ammonia. The principle is based on the ability of a
catalyst surface site to accept a single electron from an electron donor like perylene to form charge transfer complexes
and the amount of adsorbed species is measured quantitatively by UV-Vis spectroscopy. Finally, an attempt has been
made to correlate the acidity determined by the two independent methods and the catalytic activity of present systems
in the benzoylation of toluene with benzoyl chloride. Incorporation of Fe and Cr has changed the properties of Al
pillared montmorillonite. Fe pillared systems have been found to be very good catalysts for benzoylation reaction.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1363-1368
Synthesis and crystal structure of two extensively hydrogen
bonded
network of Cu(II)
Sudipta Dalai, Partha Sarathi Mukherjee+, Steven Geib & Nirmalendu Ray Chaudhuri
Two new Cu(II) coordination polymers of higher dimensionality, [Cu(L1)2](L2), [L1= N-(2hydroxyethyl)ethylenediamine, L2= fumarate dianion], (1) and [Cu(L3)2(H2O)2](L4), [L3= 1-(2aminoethyl)pyrrolidine, L4= squarate dianion], (2), have been synthesized and characterized by X-ray single crystal
analysis. Complexes (1) and (2) form 3D and 2D network respectively through extensive hydrogen bonding.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1369-1373
Electron spin resonance, magnetic and superoxide dismutase activity of
binuclear imidazolate bridged complexes
R N Patel*, K K Shukla, N Singh & K B Pandeya +
Electron paramagnetic resonance, magnetic susceptibility and superoxide dismutase (SOD) activity
measurements of imidazolate bridged [(Salval)Cu-Im-Cu(Salval)]Na, [(Salval)Cu-Im-Ni(Salval)]Na and
[(Salval)Cu-Im-Zn(Salval)]Na complexes, [where salval = salicyledenevalinate, im = imidazolate ion,] are
described. Related mononuclear copper(II) compelxes are also synthesized. The pH-dependent EPR and
electronic spectroscopic studies of frozen 50% aqueous DMSO solution of homo- and heterobinuclear
complexes have been found to be stable over the wide pH range.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1374-1379
Isomeric mixed dioxolene 2-(arylazo)pyridine complexes
of osmium(II):
Synthesis, spectra and electrochemistry
Doyel Bose, Hafijur Rahaman, Jaya Banerjee, Naba Kumar Mondal & Barindra Kumar Ghosh*
The complexes blue-violet (3) and red-violet (4) isomers of [OsX2L2] [X = Cl or Br; L (2) = 2(phenylazo)pyridine (L1) and 2-(m-tolylazo)pyridine (L2)] react smoothly with catechol and its substituted
derivative [H2Q; (1)] in boiling aqueous ethanol affording mixed tris complexes of the type [OsQL 2] [(5)
and (6), respectively]. The new complexes have been characterized by physicochemical, spectroscopic
and magnetic methods. From 1H NMR spectra (taking Me of L2 as diagnostic probe), the stereoretentivity
of the reactions is proposed. The diamagnetic complexes display a number of spin-allowed and spinforbidden charge-transfer transitions in the 1200-200 nm range. Both (5) and (6) are electroactive and
display six voltammetric responses – two oxidations and four reductions. EPR study of the
coulometrically generated one-electron oxidation product suggests the involvement of semiquinone
radical formation.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1380-1384
Synthesis and reactivity of the copper (II) complexes of N-acetophenyl-X-salicylaldimines ( = 4 or 3, X = H, 5-Br
or3-COOH ). Molecular structure of
bis-( N-4-acetophenyl-salicylaldiminato) copper(II)
Rajib Lal De , Indrajit Banerjee , Subhadra Guha+ & Alok K Mukherjee+
The copper (II) complexes of the Schiff bases, N--acetophenyl-X-salicylaldimines (  = 4 or 3, X
= H, 5-Br, 3-COOH) have been synthesised and characterised by UV-visible, IR, MS, ESR spectroscopy
and magnetic suceptibility measurements. The solid state structure of Cu(SACPN x)2 (I) determined by
single-crystal X-ray diffraction reveals a distorted square-planar metal coordination involving two imine
N- and two deprotonated phenolate O atoms of two bidentate Schiff ligands in trans- arrangement. Both
the Schiff bases and their copper (II) complexes undergo facile transamination reactions.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1385-1390
Synthesis and characterization of a chelating resin
containing ONO donor tridentate Schiff base and its
coordination compounds with copper(II),
nickel(II), cobalt(II), iron(III), zinc(II), cadmium(II),
manganese(II),
molybdenum(VI), zirconium(IV) and uranium(VI)
A Syamal, D Kumar*, A K Singh, P K Gupta, Jaipal & L K Sharma
New polystyrene supported coordination compounds have been synthesized by the reaction of
metal salt/metal coordination compound with the polystyrene supported Schiff base (PS–LH2) (obtained
by the reaction of chloromethylated polystyrene, 3-formylsalicylic acid and ethanolamine). The
compounds have the formulae: PS–LCuDMF, PS–LNi3DMF, PS–LCo3DMF, PS–LFeCl2DMF, PS–
LZnDMF, PS–LCdDMF, PS–LMn3DMF, PS–LMoO2DMF, PS–LZr(OH)22DMF and PS–
LUO2DMF (DMF = dimethylformamide). The compounds have been characterized by elemental
analyses, IR, electronic, ESR spectral and magnetic susceptibility measurements. The Cu(II), Ni(II),
Co(II), Fe(III) and Mn(II) compounds are paramagnetic while the Zn(II), Cd(II), Zr(IV), Mo(VI) and
U(VI) compounds are diamagnetic. The magnetic and ESR data indicate the magnetically dilute nature of
the metal centres. The shifts of the (C=N)(azomethine), (C–O)(phenolic) and (C–O)(alcoholic)
stretches have been monitored to find out the donor sites of PS–LH2. A square planar structure for PS–
LCuDMF; a tetrahedral structure for PS–LZnDMF and PS–LCdDMF; an octahedral structure for PS–
LNi3DMF, PS–LCo3DMF, PS–LFeCl2DMF, PS–LMn3DMF, PS–LMoO2DMF and PS–LUO2DMF
have been suggested for the compounds. PS–LZr(OH)22DMF is pentagonal bipyramidal.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1391-1396
Host-guest chromatographic behaviour of ketones in
micellar paper chromatographic separation
Zhengsheng Fu*, Guoqin Lia , Aimei Yang, Weidong Liangb & Zhiguo Wang
Separation of 14 ketone compounds by paper chromatography using pure water micellar solution of
hexadecyltrimethyl ammonium bromide (CTAB) and/or sodium dodecylsulphate (SDS) as the mobile phase have been
reported. Based on the calculated molecular structural factors (e.g. length, width and height, etc.) and the cavities of
micelles, the ketones can be divided into three molecular groups. Each group has its own characteristics and all the
groups show the suitability between the solute molecules (guest) and micelles (host). The suitability is the main driving
force of chromatographic migration and reveals the relationship between solutes’ molecular structures and the cavities
of surfactants. Furthermore, the suitability can be directly used to explore molecular structure such as sizes and
geometry.
Notes
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1397-1401
Immobilization of dithiooxamide in biopolymer and
synthetic films for possible use in optical fibre copper
probe
Anupa Murugkar, Meena Karve & Subhash Padhye*
and
R Narayanaswamy
Dithiooxamide (DTO), a metallochromogenic reagent, has been immobilized in a composite biopolymer
matrix for the quantitative determination of Cu(II) by an optical fibre method. The suitability of the biopolymer matrix
for immobilization purposes has been determined from its stability in acid and basic media and absence of leaching of
the immobilized DTO and its copper complex. Immobilization of DTO in poly(methyl)methacrylate (PMMA) alone
shows characteristics comparable to that of the biopolymer matrix, while polyvinyl alcohol (PVA), polyvinyl chloride
(PVC) and Nafion membranes are found to be unsuitable. A linear response is obtained for Cu(II) concentrations
between 1 to 5 ppm.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1402-1405
Organization of amphiphiles,
Part-II—Surface activity of polyoxyethylated alkyl phenols
at air-water interface
Lingaraj Sahoo &Pramila K Misra*
and
P Somasundaran
The surface properties of a series of polyoxyethylated alkyl phenols 1a [C8H17-O(CH2CH2O)n-H, n = 10,
30] and 1b [C9H19-O(CH2CH2O)n-H, n= 10, 15, 20, 40] have been studied through surface tension measurement by
Wilhelmy plate method. The surface pressure values calculated from surface tension data have been fitted to Gibbs
adsorption equation and the standard free energies of micellization and adsorption at air water-interface have been
calculated. The minimum area per surfactant molecule and critical micellar concentrtion reveal that both steric
constraints and hydrophobicity of the surfactant play a major role in micelle formation .
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1406-1409
Olefin epoxidation catalyzed by novel nickel(II)complexes containing tridentate Schiff-base ligands
Debabrata Chatterjee* &Sanghamitra Mukherjee
Novel Schiff base complexes of nickel(II), [NiL1(H2O)] (1) {H2L1= N-(2-hydroxyphenyl)salicylaldiimine},
[NiL2(H2O)] (2) {Happ = N-(2-hydroxyphenyl) pyridine-2-carboxaldimine}, [NiL3(H2O)] (3) {N-(2carboxyphenyl)salicylaldiimine}and [NiL4(H2O)] (4) {N-(2-carboxyphenyl)pyridine-2-carboxaldi-mine} have been
prepared and characterized by physico-chemical analysis. Complexes 1-4 are found to be active in catalyzing
hydrocarbon oxidation in the presence of single oxygen atom donors. Efficiency of NiL complex towards catalysing
epoxidation of olefins in the presence of various oxidants viz. NaOCl, KHSO 5, H2O2, pyridine N-oxide (PyO), tBuOOH, etc., has been examined and it is found that the complexes 1-4 can effectively catalyze the epoxidation of
olefins in the presence of NaOCl and KHSO5.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1410-1414
Kinetics of dissociation of tris – (2, 2– bipyridyl) and tris
– (1, 10 – phenanthroline) iron (II) complexes in the
presence of OH– in the water pools of CTAB reverse
micelles
G Venkateswarlu, P Syamala, P V Subba Rao* &K Ramakrishna
The kinetic study of the dissociation of tris (2, 2-bipyridyl) and tris (1, 10 –phenanthroline) complexes in the presence
of OH– ion in the water pools of CTAB reverse micelles in hexane-chloroform mixtures has been carried out. The
former reaction has OH– independent and dependent paths whereas the latter has only OH– dependent path. The
special property of the water pool, the lower polarity (than water), has effect on kinetics. The increase in molar ratios of
[water]/[surfactant] (= W) results in decrease in rate of the OH– independent path. on the other hand an increase in W
results in increase in rate of OH– dependent path. The kinetic analysis of this effect has been carried out considering
the effects of dielectric constant and ionic strength of water pool on the rates. The results show that increase in rate due
to decrease in ionic strength predominates over the effect of increase in dielectric constant with increase in W. The
dissociation of tris(1, 10-phenanthroline) iron(II) does not have OH– independent path and the effect of W on this
reaction is identical with that of OH– dependent path of the former reaction.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1415-1416
Synthesis and crystal structure of two-dimensional network
DB18-C-6 complex: [Na(DB18-C-6)]2[Pt(SCN)6]
Tong Wang, Jianmin Dou*a, Dacheng Li, Daqi Wang, Meimei Wu & Peiju Zheng
A novel dibenzo-18-crown-6 (DB18-C-6) complex [Na(DB18-C-6)]2[Pt(SCN)6] (1) has been
synthesized and characterized by elemental analysis, IR spectrum and X-ray diffraction analysis. The
complex belongs to triclinic, space group P-1 with cell dimensions: a = 1.2500(3), b = 1.2825(3), c =
1.9342(4) nm,  = 106.82(3),  = 102.51(3),  = 103.04(3), V = 2.7562 nm3, Z = 2, Dcalcd = 1.579 g/cm3,
F(000) = 1316, R1 = 0.0364, wR2 = 0.0771. The complex shows a two-dimensional network structure of
[Na(DB18-C-6)]+ complex cations and [Pt(SCN)6]2- complex anion bridged by Na-N interactions between
adjacent [Na(DB18-C-6)]+ and [Pt(SCN)6]2- units.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1417-1420
Studies on cerium(III) complexes of piperidin-4-ones
Kuppusamy Selvaraj* & Chinniagounder Theivarasu
Ten new cerium(III) nitrate complexes of the general formula [Ce(L) 2(NO3)2(H2O)2]NO3 with variously substituted
2,6-diphenylpiperidin-4-ones (L1)-(L10) have been prepared in ethanol and characterized by elemental analysis,
molecular weights, molar conductance, magnetic and thermal studies and infrared and NMR spectra. Molar
conductance data and van’t Hoff factor (i = 2) show that these complexes are 1:1 electrolytes. The IR spectral data
reveal the participation of water molecules and thermal studies confirm the presence of two coordinated water
molecules. IR spectra, elemental analyses and molar conductance data suggest that these complexes contain one ionic
and two bidentate nitrate groups. Although piperidin-4-ones have two coordinating sites, namely the ring nitrogen and
carbonyl group, IR and NMR spectral evidences are in favour of the ring nitrogen as the coordinating group and not the
carbonyl group, thereby indicating that these ligands are monodendate. All the observations lead to the conclusion that
cerium has a coordination number of eight in these complexes.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1421-1423
Synthesis and characterization of acetylferrocenyl
thiosemicarbazone derivatives of
dichlorobis(cyclopentadienyl)hafnium(IV)
Soumitra Kumar Sengupta*, Om Prakash Pandey, Alpana Bhatt, Vinita Srivastava & Kushal Nath Mishra
The reactions of Cp2HfCl2 with thiosemicarbazones (LH) derived from acetylferrocene and substituted
thiosemicarbazide (phenyl/4-chlorophenyl/4-nitrophenyl/4-methylphenyl thiosemi-carbazide) in various stoichiometric
ratios have been studied and the complexes of the type [Cp2HfCl(L)] are obtained. Tentative structural conclusions are
drawn for the reaction products based upon elemental analyses, electrical conductance, magnetic moment and spectral
data (UV-Vis, IR, 1H NMR and 13C NMR).
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1424-1427
Synthesis and physico-chemical studies of manganese(II), nickel(II), cobalt(II),
copper(II) and zinc(II) complexes of new 13-membered pentaazamacrocycles with
N4 donor sets
Tahir Ali Khan*, Manzoor A Rather, Ajax & K Mohamed, Khan S. Islam and Nafees Jahan
A new series of 13-membered pentaazamacrocyclic complexes of the type, [MLX2], [where M = Mn(II), Ni(II),
Co(II), Cu(II) and Zn(II); X=Cl or NO3], incorporating an N4 donor set has been prepared via the template
condensation of triethylenetetraamine, formaldehyde and 4,4'-diaminobiphenyl in 1:2:1 molar ratio in the presence of
the metal salt. The complexes have been characterized by physico-chemical and spectroscopic measurements as nonionic, octahedral species.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1428-1432
Stability studies on 12-(5’-8’-hydroxyquinolinic)methylene1,4,7,10-tetraazacyclo tridecane-11,13-dione, 5-substituted
1,10-phenanthroline-copper(II) with Cu2+ or Co2+ binuclear
mixed-coordinated systems
Xiaojun Zhao, Xuncheng Su, Encui Yang, Huakuan Lin*, Shourong Zhu, Hongwei Sun &
Yunti Chen
C
-functionalized dioxotetraamine ligands L have been designed and synthesized through simple methods,
and characterized by elemental analysis, IR, mass spectra and 1H NMR. The ligand contains two independent chelating
groups. At 25.00.1C, I=0.1moldm-3 NaNO3, pH titration has been performed to study the stability properties of L5-R-5,10-phenanthroline-Cu(II) with proton, copper(II) and cobalt(II). The ternary complexes have been shown to
possess interesting properties due to the involvement of three chelating groups, 5-substituted-1,10-phenanthroline, 8hydroxyquinolin and dioxotetraamine. In addition, potentiometric titrations have been performed to study the
protonation of L-5-R-1, 10–phenanthroline-Cu(II) (R=CH3,H,Cl,NO2) and their stability properties with copper(II) and
cobalt(II). The results show that for Cu2+ and Co2+, 8-hydroxyquinoline is a strong chelating reagent than
dioxytetraamine macrocycles. Using molecular mechanics (MM+) calculation, the stability of ternary mixed system on
Co(II)-L-5-substituted-1,10-phenanthroline-Cu(II) and Cu(II)-L-5-substituted–1,10-phenanthrolineCu(II) have been
studied and compared with the coordination ability for different coordination sites and for different metal ions (Co(II)
and Cu(II)) at the same coordination site. The results obtained from calculation agree with the experimental results
.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1433-1435
Determination of zinc in high purity gallium by differential
pulse anodic stripping voltammetry
Suvarna Sounderajan, Avanti Singh & M M Palrecha*
A simple voltammetric method has been described for the determination of trace amount of zinc in high purity
gallium metal. Differential pulse anodic stripping voltammetry (DPASV), permits a direct determination of zinc
without preliminary enrichment or separation process. Zinc can be determined to levels of 1-2 g g-1, with relative
standard deviation of about 14% in  150 mg sample of gallium.The detection limit was restricted by the amount of
zinc present in the reagent blank solution.The possible interferences due to Pb, Cd, Cu, Ni, Mn, Fe, Tl, Co, Ti, V, Al
etc have also been evaluated
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1436-1437
Spectrophotometric determination of iron in traces amount
using 5-bromo-salicylaldehyde thiosemicarbazone
G Ramanjaneyulu, P Raveendra Reddy*, V Krishna Reddy & T Sreenivasulu Reddy
A simple, sensitive and specific spectrophotometric method has been developed for the determination of
iron(II) in aqueous dimethylformamide (DMF). The metal ion reacts with 5-bromosalicylaldehyde thiosemicarbazone
(5-BSAT) forming a green coloured complex in the pH range 5.0-6.0. The complex shows maximum absorption at 385
nm. Beer’s law is obeyed in the range 0.28-5.60 µg/ml. The molar absorptivity and Sandell’s sensitivity are found to be
1.72104 l mol-1 cm-1 and 0.032 µg cm-2, respectively. The method has been employed successfully for the
determination of Fe(II) in grape leaves, multivitamin capsules and human blood.
Indian Journal of Chemistry
Vol. 41A, July 2002, pp. 1438-1440
Bismuth selective antimony(III) silicate inorganic ion–
exchanger
C Reetha1, K K Aravindakshan2* & C Janardanan1*
Antimony(III) silicate has been synthesised, characterised, and its ion exchange properties have been ascertained.
The exchanger is stable in water, alcohol, acetic acid, 1.0M HCl, 1.0M HNO3 and in aqueous solutions of LiCl, KCl,
MgCl2, CaCl2 and BaCl2. Its exchange capacities for various alkali and alkaline earth metal ions have been
determined. Also distribution coefficients for various metal ions, effect of electrolyte concentration and temperature
and pH on ion exchange capacity have been studied. The molar ratio, found from chemical analysist as 1:1, suggest
Sb2O3 2SiO2 nH2O as the empirical formula for the exchanger. Binary separations of Bi(III) from Pb(II), Cu(II),
Zn(II) and Hg(II) have been achieved from a column of the exchanger
.
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July 2002 content