Indian Journal of Chemistry

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

 

VOLUME 46A

NUMBER 5

May 2007

 

CONTENTS

 

 

723

 

Estrada index of acyclic molecules

 

 

 

 

 

 

 

  

 

 

 

Ivan Gutman*, Boris Furtula,  Biljana Glišić, Violeta Marković & Aleksander Vesel

 

 

A structure-descriptor EE, recently proposed by Estrada, is examined for the acyclic molecules.

 

 

 

729

 

A molecular orbital calculation on the structures of mono and dihydroxy benzenes and their halogen substituted species

 

 

 

 

 

 

R Amrutha*, P Haripriya, S Lakshmi & P Chandran

 

 

 

Systematic studies on structures, energies, ionization potentials of monohydroxy benzenes and dihydroxy benzenes and their halogen-substituted species have been carried out by the hybrid Hartree-Fock and Density Functional theory.  The effects of halogen substitution in these species is also reported. Halogen substitution of phenol in the ortho position bends the hydroxyl group towards the substituent atom. When accommodating the halogen atom, the regular hexagonal shape of the ring structure is distorted. Also, C-H bonds shorten as a result of halogen substitution.

 

Text Box: Current density/mA cm-2
Text Box: Potential/V vs. SCE

 

736

 

Preparation of porous manganese hydroxide film and its application in supercapacitors

 

 

 

 

 

 

 

 

 

 

 

 

Zhen Fan, Jinhua Chen*, Feng Sun, Lei Yang, Yan Xu & Yafei Kuang

 

 

 

The porous Mn(OH)2 film electrode shows excellent capacitive performance and its specific capacitance at
50 mV s-1 is calculated as 450 F g-1.

 

 

 

742

 

Effect of supports on HDS activity of Au-Pd catalysts

 

 

 

 

 

 

 

 

 

 

  

 

 

 

 

 

 

 

Zhonghua Gu, Laitao Luo* & Meiling Teng

 

 

 

The Au-Pd catalysts have been used for thiophene hydrodesulfurization (HDS). The effects of Al2O3, TiO2-Al2O3, ZrO2-Al2O3 and CeO2-Al2O3 supports on HDS activities of the Au-Pd catalysts have been investigated. The results show that Au-Pd catalysts supported on mixed oxide exhibit much higher HDS activity and stability than that of the Au-Pd/Al2O3 catalysts.

 

 

 

748

 

Simple anion receptor with imidazole and phenol groups: Forming hydrogen-bond complex with Cl-

 

 

 

 

 

 

 

Huamei Chen, Hai Lin, Zunsheng Cai & Huakuan Lin*

 

 

 

A simple anion receptor 2¢-(2²-hydroxy-3²-methoxyphenyl)imidazo[4¢,5¢-f]-1, 10-phenanthroline[5,6-f] (1) with imidazole and phenol groups has been synthesized and  its interaction investigated with anions (F-, Cl-, Br-, I-, AcO- and H2PO4-) by UV-vis and 1H NMR titrations.  Also, the change in 1H NMR titration spectra of 1 with Cl- is different from that of added AcO-, F- and H2PO4-.  1 forms supramolecular complex with Cl- as a receptor and is deprotonated with AcO-, F- and H2PO4- as a colormetric sensor. The receptor forms H-bond complex with Cl- by NH of imidazole, Hc’ of phenanthroline and H1 of phenyl.

 

 

755

 

Different approaches to calculate ideal expansibility, internal pressure and speed of sound of binary liquid mixtures, and their excess counterparts

 

Amalendu Pal

 

 

 

Different approaches are reported for estimating the ideal contribution to excess speeds of sound, internal pressures and expansibilities. These are examined here and some suitable errors are identified.

 

Notes

 

760

 

Structure, and thermal, magnetic and chemical properties of copper(II)iodoacetate monohydrate

 

 

 

 

 

 

 

 

  

 

Michael G B Drew, Rodolphe Clérac,
Senjuti De & Dipankar Datta*

 

 

 

Cu2(ICH2COO)4.2H2O has a J value of -142(1) cm-1. It reacts with 2,2¢-bipyridine (bpy) to yield [Cu(bpy)2I] I. It oxidises thiophenol to Ph-S-S-Ph under dry N2 atmosphere.

 

 

 

764

 

A new emissive Ru(II)N5O core

 

 

 

 

  

 

 

 

 

Michael G B Drew, Samik Nag & Dipankar Datta*

 

 

 

 

 

768

 

Synthesis and spectroscopic properties of some new metallatranes

 

 

 

 

 

 

 

  

 

 

Rajendra Singh Ghadwal & Anirudh Singh*

 

 

 

Six new metallatranes, Al(dmba), Ga(dmba), BuSn(dmba), Sb(dmba), Zr(dmba)(OPri), and Nb(dmba)(OPri)2 (where tris(2-oxy-3,5-dimethylbenzyl)amine, N{CH2 (3,5–Me2C6H2O)}3 is abbreviated as dmba), are reported.

 

.

 

 

772

 

Synthesis, spectroscopic and magnetic properties of nonaalkoxodistannatocobalt(II) derivatives

 

 

 

 

 

 

 

 

 

 

 

Neetu Agrawal & Anirudh Singh*

 

 

 

Nonaalkoxodistannate complexes of cobalt(II) of the types [Co{h4-Sn2(OR)9}(m-Cl)]2(R = Pri(1), Et (2)) and
[Co{h3-Sn2(OR)9}2] (R = Pri(3), Et(4)) have been prepared 
(h3 and h4 represent the tri- and tetradentate ligation of {Sn2(OR)9}, respectively).  The dimeric complexes (1) and (2) are useful precursors for the synthesis of heterobimetallic derivatives such as [Co{h4-Sn2(OPri)9}(m-OPri)]2 (5), [Co{h4-Sn2(OEt)9}(m-OEt)]2 (6), [Co{h4-Sn2(OPri)9}(m-OCH2CH2NH-CH3)]2 (7), [Co{h4-Sn2(OEt)9}(m-OCH2CH2-NHCH3)]2 (8), [Co{h4-Sn2(OPri)9}(m-OCH2CH2-OCH3)]2 (9), [Co{h4-Sn2(OEt)9}(m-OCH2CH2OCH3)]2 (10), [Co{h4-Sn2(OPri)9}
(m-OCH2CH2OC2H5)]2 (11), and [Co{h4-Sn2(OEt)9}
(m-OCH2CH2OC2H5)]2 (12).

 

 

778

 

Electrochemical behaviour of Ni(II)
l-amino acid in aqueous dimethylformamide, N-methyl formamide and formamide
media at dme

 

 

  

B S Bairwa, Monika Goyal, I K Sharma,
S Varshney & P S Verma
*

 

 

 

Polarographic technique has been used to evaluate the kinetic parameters and formation constants of Ni(II) complexes with
l-arginine, l-lysine, l-tryptophan, l-tyrosine, l-aspartic acid and
l- glutamic acid at pH 8.40±0.20 and constant ionic strength
(m= 0.1) NaClO4 in aqueous DMF, N-methyl formamide and formamide mixture at d.m.e. The kinetic parameters (K0fh, an,x) have been calculated using Meites-Israel method and its modification by Gaur and Bhargava. In all the cases a single reduction wave is obtained but in the case of Ni(II) l-lysine complex in N-methyl formamide, two waves are obtained.

 

 

783

 

Kinetic investigation of the reactions between triphenylphosphine, dialkyl acetylene dicarboxylates and NH-acid such as 7-azaindole by the UV spectrophotometry

 

 

 

 

 

 

 

S M Habibi Khorassani*, M T Maghsoodlou,
A Ebrahimi, H Roohi & M Zakarianezhad

 

 

 

Kinetic studies of the reactions between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of NH-acid, such as 7-azaindole are reported.

 

 

 

789

 

Densities, viscosities, viscosity deviations and excess thermodynamic properties of binary liquid mixtures of diethyl oxalate and dimethyl malonate with polar and non-polar solvents at 303.15 K

 

 

 

 

 

 

 

Archana Diwedi & Mukhtar Singh*

 

 

 

Densities and viscosities have been measured for the binary liquid mixtures of diethyl oxalate and dimethyl malonate with some polar and non-polar solvents, viz. ethanol, acetone, chloroform, carbon tetrachloride, benzene and toluene over the entire composition range at 303.15 K. From density and viscosity data, the values of viscosity deviations (Dh) and excess thermodynamics properties, viz. the excess molar volumes (VE) and the excess Gibbs free energies of activation of viscous flow (DG#E) of the binary mixtures have been determined at 303.15 K. The values of Dh, VE and DG#E have been fitted to Redlich-Kister polynomial equation to estimate the binary coefficients and standard deviation between the experimental and computed values.

 

 

Authors for correspondence are indicated by (*)


Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 723-728

 

Estrada index of acyclic molecules

Ivan Gutmana, Boris Furtula, Biljana Glišić, Violeta Marković & Aleksander Vesel

Received 31 December 2006; revised 5 April 2007

A structure-descriptor EE, recently proposed by Estrada, is examined. If λ1, λ2,...,λn are the eigenvalues of the molecular graph, then . In the case of trees with n vertices (that are the graph representations of alkane isomers CnH2n+2), the main structural factor influencing the differences between the EE-values has been found to be the Zagreb index Zg. The coefficient b in the regression line EE = a Zg + b is an almost perfectly linear function of n, implying that in the case of alkanes, EE linearly increases with the number of carbon atoms.

 

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 729-735

 

A molecular orbital calculation on the structures of mono and dihydroxy benzenes and their halogen substituted species

R Amrutha*, P Haripriya, S Lakshmi & P Chandran

Received 10 May 2006; revised 26 March 2007

Systematic studies on structures, energies, ionization potentials of mono hydroxy benzenes and dihydroxy benzenes and their halogen-substituted species have been carried out by the hybrid Hartree-Fock and Density Functional theory. The effects of halogen substitution in these species have been studied by comparing the results with the available experimental and theoretical investigations. Halogen substitution of phenol in the ortho position bends the hydroxyl group towards the substituent atom. When accommodating the halogen atom, the regular hexagonal shape of the ring structure is distorted. C-H bonds shorten as a result of halogen substitution. The present studies have wider scope for studying the intramolecular interactions.

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 736-741

 

Preparation of porous manganese hydroxide film and its application in supercapacitors

Zhen Fan, Jinhua Chen*, Feng Sun, Lei Yang, Yan Xu & Yafei Kuang

Received 18 January 2007; revised 25 March 2007

Preparation of a manganese hydroxide film by electrochemically induced deposition method is reported here. The morphology and crystal structure of the film have been investigated by scanning electron microscopy and X-ray diffraction, respectively. The possible deposition mechanism of the film is also discussed. Moreover, the capacitive properties of the film have been evaluated by cyclic voltammetry and galvanostatic charge-discharge method. The results indicate that the morphology of the deposits depends on the amount and size of evolved H2 bubbles, which can be adjusted by changing the composition of electrolyte and deposition current density. The capacitive properties of film are affected by the deposition parameters. The film prepared under the optimum deposition conditions shows excellent capacitive properties: high specific capacitance (493 F g-1 in 0.1 M Na2SO4 aqueous solution from 0 to 1 V at a current density of 1 mA cm-2), high electrochemical reversibility and excellent long-term charge-discharge cycle stability (2.2% loss of the specific capacitance observed at the 2000th cycle under the charge-discharge current density of 10 mA cm-2).

IPC Code: Int. Cl.8 C25B1/21; C01G45/02; H01G4/33

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 742-747

 

Effect of supports on HDS activity of Au-Pd catalysts

Zhonghua Gu, Laitao Luo* & Meiling Teng

Received 10 July 2006; revised 20 March 2007

The Au-Pd catalysts have been used successfully for thiophene hydrodesulfurization (HDS). The effects of Al2O3, TiO2-Al2O3, ZrO2-Al2O3 and CeO2-Al2O3 supports on HDS activities of Au-Pd catalysts have been investigated. The results show that Au-Pd catalysts supported on mixed oxide exhibit much higher HDS activity and stability than that of the Au-Pd/Al2O3 catalyst. TiO2-Al2O3 is the best support among these mixed oxides. As compared with Au-Pd/Al2O3 catalyst, Au-Pd/TiO2-Al2O3 catalyst has higher acid density and acid strength, and active surface area to absorb higher amounts of H2 and CO.

IPC Code: Int. Cl.8 B01J23/44; B01J23/52; C10G25/05

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 748-754

 

Simple anion receptor with imidazole and phenol groups: Forming hydrogen-bond complex with Cl-

Huamei Chen, Hai Lin, Zunsheng Caia& Huakuan Lin*

Received 21 Febuary 2007; revised 4 April 2007

A simple anion receptor 2¢-(2²-hydroxy-3²-methoxyphenyl)imidazo[4¢,5¢-f]-1, 10-phenanthroline[5,6-f] (1) with imidazole and phenol groups has been synthesized and its interaction investigated with anions (F-, Cl-, Br-, I-, AcO- and H2PO4-) by UV-vis and 1H NMR titrations. Added with Cl-, the change of UV-vis spectra of 1 is different from that of added AcO-, F- and H2PO4-. Also, the change of 1H NMR titration spectra of 1 with Cl- is different from that of added AcO-, F- and H2PO4-. 1 forms supramolecular complex with Cl- as a receptor and is deprotonated with AcO-, F- and H2PO4- as a colormetric sensor. The receptor forms H-bond complex with Cl- by NH of imidazole, Hc’ of phenanthroline and H1 of phenyl. As an acid proton donor, the protons of NH of imidazole and OH of phenol are too acidic to form hydrogen-bond complex with AcO-, F- and H2PO4-. So, the interaction of 1 with AcO-, H2PO4- and F- is acid-basic reaction. The affinity to anions of NH is dramatically more powerful than that of OH.

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 755-759

 

Different approaches to calculate ideal expansibility, internal pressure and speed of sound of binary liquid mixtures, and their excess counterparts

 

Amalendu Pal

Received 29 July 2005; rerevised 19 March 2007

The excess properties are often discussed in terms of molecular interaction in binary liquid mixtures. Different approaches are reported for estimating the ideal contribution to excess speeds of sound, internal pressures and expansibilities. In this overview, these are examined and some suitable errors are identified.

Indian Journal of Chemistry

 

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 760-763

 

Structure, and thermal, magnetic and chemical properties of copper(II)iodoacetate monohydrate

Michael G B Drew, Rodolphe Clérac, Senjuti De  & Dipankar Datta*

Received 21 July 2006; revised 13 March 2007

Reaction of iodoacetic acid with cupric carbonate in water in dimmed light yields green Cu(ICH2COO)2.H2O (1). From X-ray crystallography, it is found to be a tetra-acetato bridged copper(II) dimer with the water molecules occupying the apical positions. In thermogravimetry, the coordinated water molecules are lost in the temperature range 50-100°C. From magnetic susceptibility measurements in the temperature range 300-1.8 K, the exchange coupling constant J is found to be -142(1) cm-1 and g = 2.18(2) with the spin Hamiltonian H = -2J{SCu1·SCu2}. It reacts with 2,2¢-bipyridine (bpy) to yield [Cu(bpy)2I]I. It oxidises thiophenol to Ph-S-S-Ph under dry N2 atmosphere.

IPC Code: Int.Cl.8 C07F1/08

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 764-767

 

A new emissive Ru(II)N5O core

Michael G B Drew, Samik Nag & Dipankar Datta*

Received 21 July 2006; revised 13 March 2007

From the reaction of cis-Ru(1,10-phenanthroline)2Cl2.2H2O with 2-picolinic acid in 1:1 molar ratio in degassed methanol-water mixture, [Ru(1,10-phenanthroline)2(2-picolinate)]PF6.H2O (1) has been isolated as a red compound by adding excess of NH4PF6. Single crystal X-ray crystallography shows that the metal in 1 has an octahedral N5O coordination sphere. Complex 1 displays 1MLCT bands in the 400-500 nm region in acetonitrile. Upon excitation at 435 nm, complex 1 gives rise to a broad emission band at 675 nm in acetonitrile at room temperature with a quantum yield of 0.0022. The energy of the MLCT state in 1 is estimated as 1.99 eV. Since, from cyclic voltammetry, the ground state potential of the Ru(II/III) couple in 1 is found to be 1.01 V vs NHE, the potential of the same couple in the excited state is calculated as -0.98 V vs NHE. The emissive state in 1 seems to be the triplet Ru(II) ® 1,10-phenanthroline charge transfer state.

IPC Code: Int. Cl.8 C07F15/00

 

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 768-771

 

Synthesis and spectroscopic properties of some new metallatranes

 

Rajendra Singh Ghadwal & Anirudh Singh*

Received 20 April 2006; revised 22 March 2007

Six new metallatranes, Al(dmba) (1), Ga(dmba)(2), BuSn(dmba) (3), Sb(dmba) (4), Zr(dmba)(OPri) (5), and Nb(dmba)(OPri)2 (6) (where tris(2-oxy-3,5-dimethylbenzyl)amine, N{CH2 (3,5–Me2C6H2O)}3 is abbreviated as dmba), have been prepared by the equimolar interactions of tris(2-hydroxy-3,5-dimethylbenzyl)amine,(H3dmba) with the corresponding metal alkoxides. Complex (6) reacts with 2,3-dimethyl-2,3-butanediol, (HOGOH) in 1:1 molar ratio to afford the mixed-ligand complex Nb(dmba)(OGO) (7). All these complexes have been charac­terized by elemental analysis, molecular weight determinations and spectroscopic (IR and 1H-, 27Al-, 119Sn- NMR) studies.

IPC Code: Int. Cl.8 C07F5/00; C07F5/06; C07F7/00; C07F7/22; C07F9/00; C07F9/90

 

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 772-777

 

Synthesis, spectroscopic and magnetic properties of nonaalkoxodistannatocobalt(II) derivatives

Neetu Agrawal & Anirudh Singh*

Received 4 May 2006; revised 22 March 2007

Nonaalkoxodistannate complexes of cobalt(II) of the types [Co{h4-Sn2(OR)9}(m-Cl)]2(R = Pri(1), Et (2)) and [Co{h3-Sn2(OR)9}2] (R = Pri(3), Et(4)) have been prepared by the interactions of anhydrous CoCl2 with NaSn2(OR)9(R = Pri, Et) in 1:1 and 1:2 molar ratios, respectively (where h3 and h4 represent the tri- and tetradentate ligation of {Sn2(OR)9}, respectively).  The dimeric chloro(nonaalkoxodistannato)cobalt(II) complexes [Co{h4-Sn2(OR)9}(m-Cl)]2, (1) and (2) have been found to be useful precursors for the synthesis of a variety of interesting heterobimetallic derivatives such as [Co{h4-Sn2(OPri)9}(m-OPri)]2 (5), [Co{h4-Sn2(OEt)9}(m-OEt)]2 (6), [Co{h4-Sn2(OPri)9}(m-OCH2CH2NH-CH3)]2 (7), [Co{h4-Sn2(OEt)9}(m-OCH2CH2-NHCH3)]2 (8), [Co{h4-Sn2(OPri)9}(m-OCH2CH2-OCH3)]2 (9), [Co{h4-Sn2(OEt)9}(m-OCH2CH2OCH3)]2 (10), [Co{h4-Sn2(OPri)9}(m-OCH2CH2OC2H5)]2 (11), and [Co{h4-Sn2(OEt)9}(m-OCH2CH2OC2H5)]2 (12). All these complexes (1)-(12) are highly moisture-sensitive, coloured solids, soluble in organic solvents. Molecular weights determined cryoscopically in benzene solutions show dimeric nature for (1),(2),(5)-(12) and monomeric behaviour for (3) and (4). These complexes have been characterized by elemental analyses, spectroscopic (UV-vis, IR) and magnetic measurements.

IPC Code: Int. Cl.8 C07F7/22; C07F15/06

Indian Journal of Chemistry

Vol. 46A, May. 2007, pp. 778-782

 

Electrochemical behaviour of Ni(II) l-amino acid in aqueous dimethylformamide, N-methyl formamide and formamide media at dme

B S Bairwa, Monika Goyal, I K Sharma, S Varshney & P S Verma*

Received 17 July 2006; revised 9 Maarch 2007

Polarographic technique has been used to evaluate the kinetic parameters and formation constants of Ni(II) complexes
with l-arginine, l-lysine, l-tryptophan, l-tyrosine, l- aspartic acid and l- glutamic acid at pH 8.40±0.20 and constant ionic strength (m= 0.1) NaClO4 in aqueous DMF, N-methyl formamide and formamide mixture at d.m.e. The reduction of all these complexes is found to be irreversible and hence the kinetic parameters
(K0fh, an,x) of these complexes have been calculated using Meites-Israel method and its modification by Gaur and Bhargava. In all the cases a single reduction wave is obtained but in the case of Ni(II) l-lysine complex in N-methyl formamide, two waves are obtained. This could possibly be due to the fact that the complex may have split in solution forming the aquo nickel complex, which reduces at sufficiently negative potential to the corresponding complex. One wave is found to be diffusion controlled while the other is a kinetic wave.

IPC Code: Int. Cl.8 C07C229/76; G01N27/48

 

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 783-788

 

Kinetic investigation of the reactions between triphenylphosphine, dialkyl acetylenedicarboxylates and NH-acid such as 7-azaindole by the UV spectrophotometry

 

S M Habibi Khorassani*, M T Maghsoodlou, A Ebrahimi, H Roohi & M Zakarianezhad

Received 27 March 2006;rerevised 30 March 2007

Kinetic studies of the reactions between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of NH-acid, such as 7-azaindole are reported here. Kinetic parameters of the reactions have been monitored by UV spectrophotometery. The second order fits have been automatically drawn and the values of the second order rate constant (k2) calculated using standard equations within the program. At the temperature range studied, dependence of second order rate constant (Ln k2) on reciprocal temperature is in agreement with Arrhenius equation. This provides the relevant plots to calculate the activation energy of all reactions. Studies on the effect of solvent, structure of reactants (different alkyl groups within the dialkyl acetylenedicarboxylates) and also concentration of reactants on the rate of reactions have been made. Proposed mechanism has been confirmed according to the obtained results and steady state approximation and first step (k2) of reaction recognized as the rate determining step on the basis of experimental data.

Indian Journal of Chemistry

Vol. 46A, May 2007, pp. 789-794

 

Densities, viscosities, viscosity deviations and excess thermodynamic properties of binary liquid mixtures of diethyl oxalate and dimethyl malonate with polar and non-polar solvents at 303.15 K

Archana Diwedi & Mukhtar Singh*

Received 4 January 2007; revised 26 March 2007

Densities and viscosities have been measured for the binary liquid mixtures of diethyl oxalate and dimethyl malonate with some polar and non-polar solvents, viz. ethanol, acetone, chloroform, carbon tetrachloride, benzene and toluene over the entire composition range at 303.15 K. From density and viscosity data, the values of viscosity deviations (Dh) and excess thermodynamics properties, viz. the excess molar volumes (VE) and the excess Gibbs free energies of activation of viscous flow (DG#E) of the binary mixtures have been determined at 303.15 K. The values of Dh, VE and DG#E have been fitted to Redlich-Kister polynomial equation to estimate the binary coefficients and standard deviation between the experimental and computed values. On correlating the viscosities of the binary liquid mixtures with the equations of Nissan-Grunberg and McAllister, it is concluded that the viscosities are best correlated with McAllister equation.