Indian Journal of Chemistry

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

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

 

 

VOLUME 53A

NUMBER 3

MARCH 2014

 

CONTENTS

 

 

257

 

Dehydration of oxime on the self-architected MFI structure

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Hariharan , M Palanichamy & B Viswanathan*

 

 

 

Template-free MFI phase formation is reported. High conversion (51%) in the catalytic dehydration of oxime shows that the synthesized MFI zeolite possesses strong Bronstead acid sites.

 

 

GA.tiff

 

 

 

265

 

One-pot hydrothermal synthesis of Fe3O4/reduced graphene oxide nanocomposite for enhanced lithium storage

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Xiao Zhang*, Bin Jiang, Yaping Xie & Feng Du

 

 

 

Well-dispersed Fe3O4 nanoparticles are deposited on the surface of rGO sheets by hydrothermal method. The Fe3O4/rGO nanocomposite exhibits significantly improved reversible capability, recycling stability and rate performance as compared with bare Fe3O4 when tested as the anode in lithium ion batteries.

 

 

 

 

274

 

Synthesis and characterization of tungsten carbonyl complexes containing thioamides

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Abdur R Miah, Jagodish C Sarker,
Subas Rajbangshi, Shariff E Kabir*, Shishir Ghosh & Tasneem A Siddiquee
*

 

 

 

Several tungsten pentacarbonyl complexes have been synthesized from the reactions between [W(CO)5(NCMe)] and thioamides.

 

 

 

 

281

 

Quantum chemical studies on the structure and performance properties of 2,5,2'-triazido-1,1'-azo-1,3,4-triazole

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Li Xiao-Hong*, Mei Zheng, Cui Hong-Ling &
Zhang Rui-Zhou

 

 

 

DFT analysis of the structural and energetic properties of
2,5,2'-triazido-1,1'-azo-1,3,4-triazole show that the detonation velocity and pressure of the title compound are comparable to those of RDX.
Bond dissociation calculations show that N5-N6 bond is the trigger bond during pyrolysis.

 

 

LUMO+1

 

 

 

Notes

 

288

 

DFT investigations of the Diels-Alder reaction of fulvene with tetracyclo[6.2.2.13,6.02,7]trideca-4,9,11-triene-9,10-dicarboxylic anhydride dienophile

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rza Abbasoglu*, Abdurrahman Atalay &
Ahmet Şenocak

 

 

 

Mechanism and stereochemistry of the Diels-Alder reaction of fulvene with tetracyclo[6.2.2.13,6.02,7]trideca-4,9,11-triene-9,10-dicarboxylic anhydride are investigated by quantum chemical calculations.

 

 

 

 

 

294

 

In situ preparation, structure, fluorescence and TDDFT calculations of [(CdCl3)2(μ2-HCl)]2-[CdCl4(HCl)][N,N′-dimethyl-4,4′-bipyridinium]3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Wen-Tong Chen*, Rong-Hua Hu, Zhi-Gang Luo, Hua-Long Chen, Xian Zhang & Juan Liu

 

 

 

[(CdCl3)2(μ2-HCl)]2-[CdCl4(HCl)][N,N-dimethyl-4,4-bipyridinium]3 crystallizes in the P31c space group of hexagonal system.
The [(CdCl3)2(μ2-HCl)] anion, [CdCl4(HCl)] anion and
[N,N-dimethyl-4,4-bipyridinium]2+ cation are interlinked through hydrogen bonding interactions to yield a three-dimensional supramolecular network. The compound displays an intensive emission band in the green region, which originates mainly from the ligand-to-ligand charge transfer transition, accompanied by a minor metal-to-ligand charge transfer transition.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

Indian Journal of Chemistry

Vol. 53A, March 2014, pp. 257-264

 

 

Dehydration of oxime on the self-architected MFI structure

S Hariharana, M Palanichamyb & B Viswanathana, *

aNational Center for Catalysis Research, Indian Institute of Technology- Madras, Chennai 600 025, India

Email: bvnathan@iitm.ac.in

bDepartment of Chemical Engineering, Hanseo University, Haemi-myun, Seosan-si, Chungcheongnam-do,
South Korea 356706

Received 20 January 2014; revised and accepted 24 February 2014

Na-ZSM-5 (Si/Al= 50, 100 and 150) zeolites have been synthesized in alkaline pH of 10.5 ± 0.2 by hydrothermal process without the use of template and with tetraethyl orthosilicate as silicon source. The MFI phase formation is confirmed under various synthesis conditions. The synthesized material possesses strong acid sites and the Na-ZSM-5 catalyst ion exchanged to H-ZSM-5 has been can be used to investigate the dehydration of 4-Cl-benzaldoxime. The dehydration of benzaldoxime is confirmed by the observing nitrile stretch at 2400 cm-1. The conversion levels ( ̴ 51%) show that the synthesized catalyst possesses strong Bronsted acid sites.

Keywords: Catalysts, Zeolites, Aluminosilicates, Benzaldoxime, Dehydration

 

Indian Journal of Chemistry

Vol. 53A, March 2014, pp. 265-273

 

 

One-pot hydrothermal synthesis of Fe3O4/reduced graphene oxide nanocomposite for enhanced lithium storage

Xiao Zhang*, Bin Jiang, Yaping Xie & Feng Du

State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering,
Qingdao University of Science and Technology, Qingdao 266042, PR China

Email: zhx1213@126.com

Received 1 October 2013; revised and accepted 20 February 2014

A simple one-pot hydrothermal approach is employed for the fabrication of Fe3O4/reduced graphene oxide (rGO) nanocomposite as the superior anode material for lithium ion batteries (LIBs). The reduction of graphene oxide sheets into rGO is achieved successfully during the hydrothermal process. The well-dispersed Fe3O4 nanoparticles are decorated on the surface of rGO sheets densely and homogeneously. With the introduction of rGO, the Fe3O4/rGO nanocomposite exhibits significant improvement in the reversible capability, cycling stability and rate performance in comparison with bare Fe3O4, delivering a high capacity of 884 mAh g-1 at a current density of 200 mA g-1 after 100 cycles. This hybrid composite is a potential candidate as anode material of high performance rechargeable lithium ion batteries.

Keywords: Composites, Nanocomposites, Hydrothermal synthesis, Iron oxides, Reduced graphene oxide, Ferromagnetism, Lithium ion battery

 

Indian Journal of Chemistry

Vol. 53A, March 2014, pp. 274-280

 

 

Synthesis and characterization of tungsten carbonyl complexes
containing thioamides

Abdur R Miaha, Jagodish C Sarkera, Subas Rajbangshia, Shariff E Kabira, *, Shishir Ghosha &
Tasneem A Siddiqueeb, *

aDepartment of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh

bDepartment of Chemistry, Tennessee State University, 3500 John A. Merritt Blvd, Nashville, TN 37209, USA

Email: skabir_ju@yahoo.com

Received 27 November 2013; revised and accepted 21 February 2014

Tungsten pentacarbonyl complexes are isolated from the reactions between [W(CO)5(NCMe)] and thioamides, the former being generated in situ upon addition of  equimolar amount of Me3NO into an acetonitrile solution of W(CO)6. Room temperature reactions between [W(CO)5(NCMe)] and acyclic thioamides such as thioacetamide and benzamide afford [W(CO)51-(S)-RCSNH2}] in which the thioamides are coordinated to tungsten through sulfur. Similar S-coordinated complexes, namely, [W(CO)51-(S)-thiolactam}] are also isolated from the reactions with cyclic thioamides or thiolactams under the same reaction conditions. All the new complexes have been adequately characterized by spectroscopic data together with single crystal X-ray diffraction studies for four complexes.

Keywords: Organometallic chemistry, Tungsten, Carbonyls, Thioamides, Heterocyclic thiones, X-ray structures

 

Indian Journal of Chemistry

Vol. 53A, March 2014, pp. 281-287

 

 

Quantum chemical studies on the structure and performance properties of
2,5,2
'-triazido-1,1'-azo-1,3,4-triazole

Xiao-Hong Lia, b, *, Mei Zhenga, Hong-Ling Cuia & Rui-Zhou Zhanga

aCollege of Physics and Engineering, Henan University of Science and Technology, Luoyang 471003, China

bLuoyang Key Laboratory of Photoelectric Functional Materials, Henan University of Science and Technology,
Luoyang 471023, China

Email: lorna639@126.com

Received 2 December 2013; revised and accepted 18 February 2014

Density functional theoretical method has been used to investigate the IR spectrum, heat of formation and thermal stability of a new energetic material, viz., 2,5,2'-triazido-1,1'-azo-1,3,4-triazole. The detonation velocity and pressure are evaluated using the Kamlet-Jacobs equations, based on the theoretical density and heat of formation. The bond dissociation energies for the weakest bonds have been analyzed to investigate the thermal stability of the title compound. The results show that the heat of formation of the title compound is much larger than that of RDX and HMX. The detonation velocity and pressure of the title compound are lower than those of HMX, but comparable to those of RDX. Bond dissociation calculations show that the N5-N6 bond is the trigger bond during pyrolysis.

Keywords: Density functional theory calculations, 2,5,2'-Triazido-1,1'-azo-1,3,4-triazole, Triazoles,
  Detonation properties, Bond dissociation energy, Frontier molecular orbitals

 

Indian Journal of Chemistry

Vol. 53A, March, 2014, pp. 288-293

 

 

DFT investigations of the Diels-Alder reaction of fulvene with tetracyclo[6.2.2.13,6.02,7]trideca-4,9,11-triene-9,10-dicarboxylic
anhydride dienophile

Rza Abbasoglu*, Abdurrahman Atalay & Ahmet Şenocak

Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey

Email: rabbas@ktu.edu.tr

Received 3 June 2013; revised and accepted 30 January 2014

The geometry and the electronic structure of the tetracyclo- [6. 2.2.13,6.02,7]trideca-4,9,11-triene-9,10-dicarboxylic anhydride (TTDA) have been investigated by DFT/B3LYP and DFT/B3PW91 methods using the 6-31G(d,p) and 6-311G(d,p) basis sets. Anhydride double bond of TTDA molecule is anti-pyramidalized. Potential energy surface of addition reaction of fulvene to TTDA molecule (syn,endo-, syn,exo-, anti,endo- and anti,exo-addition) is calculated by B3LYP/6-31G(d,p) method and configurations (transition state and product) corresponding to stationary points (saddle point and minima) are determined. Kinetic and thermodynamic parameters of cycloaddition reactions have also been calculated. Syn addition reactions have lower activation energies, enthalpies, entropies and free energies than anti addition reactions. Activation energies of syn,endo- and syn,exo-addition reactions are 25.032 and 23.210 kcal mol-1, respectively, while the anti,endo-addition reaction has the largest activation energy (28.763 kcal mol-1). According to theoretical calculations, syn addition reactions should take place in line with experimental conditions. There is a correlation between the syn-π-face selectivity of the cycloaddition reaction and the pyramidalization of anhydride double bond of the TTDA molecule.

Keywords: Theoretical chemistry, Density functional calculation, Diels-Alder reaction, Syn-π-face selectivity, Pyramidalization, Cycloaddition, Steric hindrance

 

Indian Journal of Chemistry

Vol. 53A, March 2014, pp. 294-298

 

 

In situ preparation, structure, fluorescence and TDDFT calculations of [(CdCl3)2(μ2-HCl)]2-[CdCl4(HCl)][N,N′-dimethyl-4,4′-bipyridinium]3

Wen-Tong Chena, b,*, Rong-Hua Hua, Zhi-Gang Luoa, Hua-Long Chena, Xian Zhanga & Juan Liub

 

aInstitute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji’an, Jiangxi 343009, China

bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences, Fuzhou, Fujian 350002, China

Email: cwtqq@aliyun.com

Received 23 December 2013; revised and accepted 24 February 2014

A novel cadmium-4,4′-bipyridinium compound, [(CdCl3)2(μ2-HCl)]2[CdCl4(HCl)][N,N′-dimethyl-4,4′-bipyridinium]3 (1) in which the N,N′-dimethyl-4,4′-bipyridinium moiety is obtained in situ, has been synthesized via a solvothermal reaction and characterized by X-ray diffraction analyses. Compound (1) crystallizes in the P31c space group of rhombohedral system. The [(CdCl3)2(μ2-HCl)] anion, [CdCl4(HCl)] anion and [N,N′-dimethyl-4,4′-bipyridinium]2+ cation are interlinked through hydrogen bonding interactions to yield a three-dimensional supramolecular network. Fluorescence investigation reveals that compound (1) displays an intensive emission band in the green region. In combination with the theoretical studies, it may be concluded that the emission band originates mainly from the ligand-to-ligand charge-transfer transition, accompanied by a minor metal-to-ligand charge-transfer (MLCT) transition.