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 54A

NUMBER 4

APRIL 2015

 

CONTENTS

 

 

451

 

Synthesis of 2-propylheptanol from 1-pentanal in a single pot using bi-functional ruthenium hydrotalcite catalyst in batch and flow reactors

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sumeet K Sharma & Raksh V Jasra*

 

 

 

Catalytic activity of ruthenium containing hydrotalcite sample has been studied for one pot synthesis of 2-propylheptan-1-ol from
1-pentanal in batch and fixed bed reactors. In continuous flow reactor, 90% conversion of 1-pentanal with 41% selectivity to
2-propylheptan-1-ol is obtained.

 

 

 

 

459

 

Density functional theory and reduced density gradient investigations into HCN adsorption on the Co(100) and Co(110) surfaces

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ying-Hu Zhao*, Ying-Yong Wang, Li Gao & Hui Song

 

 

 

Parallel adsorption configuration is energetically favored as compared with the perpendicular mode, with the former weakening the strength of the C≡N bond to a larger extent than the latter.

 

 

 

 

 

 

469

 

Crystallization of amorphous silica to silicalite-1: Effect of nature of silica sources and tetrapropylammonium hydroxide concentration

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M S M Kamil, K Manikandan, S P Elangovan,
Masaru Ogura, K K Cheralathan
*

 

 

 

Dry gels obtained from different sources of silica have been crystallized into silicalite-1 by steam assisted conversion. Nature of the source and concentration of tetrapropylammonium hydroxide have a significant effect on shape, size and pore structure
of silicalite-1. N2 adsorption results reveal that the prepared silicalite-1 samples possess a wide pore size distribution and
apart from zeolitic micropores comprise pores in meso- and
macro- pore regions.

 

 

 

Notes

 

478

 

Supramolecular interactions in mononuclear iron(III) complex derived from a diamide ligand: Spectroscopic and electrochemical properties

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Suvendu Samanta, Amit Kumar Dutta &
Papu Biswas
*

 

 

 

The mononuclear iron(III) complex, [Fe(L)3]DMF (where HL is 2,6-bis[(N-phenyl)amido]-4-methylphenol]), crystallizes in the triclinic space group P-1(2). X-ray crystal structure reveals molecular units that are linked through intermolecular hydrogen-bonding involving amide nitrogens and oxygens, giving rise to
a one-dimensional chain structure.

 

 

 

 

 

 

484

 

Oxidation of metformin with alkaline chloramine-B: Delineation of reaction mechanism and kinetic modeling

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Nirmala Vaz*, A S Manjunath & Puttaswamy

 

 

 

The kinetics and mechanism of oxidation of metformin hydrochloride with chloramine B have been investigated in alkaline medium at 308 K. The reaction rate shows a first order dependence of rate each on [CAB]o and [MET]o, and an inverse-first order dependence on [OH-]. The conjugate acid (PhSO2NHCl) is postulated as the reactive oxidizing species.

 

 

 

 

 

489

 

Photoluminescence and theoretical study of [1(Cd2Cl6)][2(CdCl4)][3(N,N′-dimethyl-4,4′-bipyridinium)]

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Zhong-Liang Yao, Wen-Tong Chen* & Rong-Hua Hu

 

 

 

A novel cadmium chloride-4,4-bipyridinium compound, namely [1(Cd2Cl6)][2(CdCl4)][3(N,N′-dimethyl-4,4′-bipyridinium)] in which the N,N-dimethyl-4,4-bipyridinium has been prepared in situ, has been obtained through solvothermal reaction. The compound contains a one-dimensional infinite 1(Cd2Cl6) chain, CdCl42 anions and [N,N-dimethyl-4,4-bipyridinium]2+ cations, interlinked via hydrogen bonding interactions to yield a three-dimensional supramolecular framework.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 54A, April 2015, pp. 451-458

 

 

Synthesis of 2-propylheptanol from 1-pentanal in a single pot using
bi-functional ruthenium hydrotalcite catalyst in batch and flow reactors

Sumeet K Sharma & Raksh V Jasra*

Reliance Technology Group, Reliance Industries Limited, Vadodara, 391 346, Gujarat, India

Email: rakshvir.jasra@ril.com (RVJ)/ sumeetsharma036@gmail.com (SKS)

Received 5 January 2015; accepted 24 March 2015

Ruthenium containing hydrotalcite (Ru-HT) has been synthesized and used as a bi-functional catalyst in batch and continuous flow fixed bed reactor for aldol condensation of 1-pentanal followed by hydrogenation of aldol condensation product in a single pot without changing the reaction conditions. Activated Ru-HT catalyst shows higher conversion of 1-pentanal (83%) than as-synthesized Ru-HT sample (59% conversion of 1-pentanal) for aldol condensation of 1-pentanal. Higher catalytic activity of activated Ru-HT catalyst is observed under solvent free conditions as compared to methanol as the solvent.

Keywords: Catalysts, Bifunctional catalysts, Hydrogenation, Aldol condensation, Ruthenium, Hydrotalcites,
1-Pentanal

 

Indian Journal of Chemistry

Vol. 54A, April 2015, pp. 459-468

 

 

Density functional theory and reduced density gradient investigations into
HCN adsorption on the Co(100) and Co(110) surfaces

Ying-Hu Zhaoa, *, Ying-Yong Wangb, Li Gaoa & Hui Songa

aSchool of Chemical and Environment Engineering, North University of China, Taiyuan 030051, China

Email: tiger5889@126.com

bState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences,
Taiyuan 030001, China

Received 19 September 2014; revised and accepted 12 March 2015

Thirteen kinds of adsorptions of HCN on the Co(100) and Co(110) surfaces at the 1/4 monolayer coverage and the reduced density gradients (RDGs) are investigated using the density functional theory. For Co(100), the adsorption energy of the most stable configuration (where HCN locates at the fourfold site with the C≡N bonded to four Co atoms) is 1.836 eV. On Co(110), the bonding energy in the most favored adsorption configuration (in which HCN locates at the fourfold-long site) is 1.580 eV. The parallel adsorption configuration is energetically favored as compared with the perpendicular mode and the former weakens the strength of C≡N bond to a larger extent than the latter. Thus, the greater activation of the C≡N bond may be found in the parallel configuration and hydrogenation reaction may be easier in the parallel configuration in which the adsorbed HCN becomes non-linear. The binding mechanism of HCN on the Co(100) and Co(110) surfaces is analyzed by Mulliken charge population and the density of states in HCN. The adsorption and metallic-bonding interactions are shown by the low density and low-gradient spike at negative values, while the low density and low-gradient region for the sterically crowded Co atoms remains at positive values indicating repulsion and steric effects.

Keywords: Theoretical chemistry, Density functional calculations, Reduced density gradient, Adsorption,
HCN adsorption, Cobalt surfaces

 

 

 

Indian Journal of Chemistry

Vol. 54A, April 2015, pp. 469-477

 

 

Crystallization of amorphous silica to silicalite-1: Effect of nature of silica sources and tetrapropylammonium hydroxide concentration

M S M Kamila, K Manikandana, S P Elangovanb, Masaru Ogurac, K K Cheralathana, *

aMaterials Chemistry Division, School of Advanced Sciences, VIT University, Vellore, 632 014, India

Email: cheralathan.k@vit.ac.in

bDepartment of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan

cInstitute of Industrial Science, The University of Tokyo, Komaba 4-6-1, Meguro, Tokyo 153-8505, Japan

Received 29 April 2014; revised and accepted 23 March 2015

Dry gels obtained from different sources of silica such as SBA-15, SBA-16, fumed silica and tetraethyl orthosilicate have been crystallized into silicalite-1 by steam assisted conversion and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy , nitrogen adsorption, and high resolution scanning electron microscopy. The results show that the nature of source and concentration of tetrapropylammonium hydroxide have a significant effect on shape, size and pore structure of silicalite-1. 29Si MAS NMR spectra of the dry gels obtained from different sources show that Si environment in these gels is similar. However, the morphology of silicalite-1 prepared under same experimental conditions is found to differ for different sources. Further, it is observed that silicalite-1 particles obtained from same source but under different TPAOH concentrations, exhibit different shapes and sizes. N2 adsorption results reveal that the prepared silicalite-1 samples possess a wide pore size distribution and comprise pores in meso- and macro-pore regions, apart from zeolitic micropores.

Keywords: Zeolites, Mesoporous materials, Macroporous materials, Silicalite-1, Silica

 

Indian Journal of Chemistry

Vol. 54A, April 2015, pp. 478-483

 

 

Supramolecular interactions in mononuclear iron(III) complex derived from a diamide ligand: Spectroscopic and electrochemical properties

Suvendu Samanta, Amit Kumar Dutta & Papu Biswas*

Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur,
Howrah 711 103, West Bengal, India

Email: papubiswas_besus@yahoo.com

Received 11 November 2014; revised and accepted 26 March 2015

The diamide ligand, 2,6-bis[(N-phenyl)amido]-4-methylphenol (HL), has been used to synthesize a mononuclear iron(III) complex [Fe(L)3]DMF and characterized by elemental analyses, IR, UVvis spectroscopy, cyclic voltammetry and finally by Xray crystallography. X-ray diffraction analysis reveals that the complex crystallizes in the triclinic space group P-1(2) with a = 12.4923(15) , b= 13.5095(16), c = 19.296(2) , α = β = 86.451(2),
γ = 66.5850(10), V = 2980.1(6)3and Z = 2 with the central iron(III) ion in distorted octahedral geometry. The complex shows extensive intra- and intermolecular hydrogen bonding between each molecular units as well as solvent molecules giving rise to a two dimensional assembly. It also exhibits intermolecular pp interaction between the aromatic rings with centroid distances of around 3.55 . In cyclic voltammetric studies, the iron(III) complex exhibits one quasi-reversible reduction at E1/2 = +0.046 V versus Ag/AgCl (DEp = 0.092 V) due to a metal-centreed FeIII/FeII reduction.

Keywords: Coordination chemistry, X-ray crystallography, Intermolecular hydrogen bonding, pp stacking, Diamides, Iron

Indian Journal of Chemistry

Vol. 54A, April 2015, pp. 484-488

 

 

Oxidation of metformin with alkaline chloramine-B: Delineation of reaction mechanism and kinetic modeling

Nirmala Vaza,*, A. S. Manjunathab & Puttaswamyb

aDepartment of Chemistry, Jyoti Nivas College Autonomous, Bangalore 560 095, India

Email: nirmavaz2005@yahoo.co.in

bDepartment of Chemistry, Central College Campus, Bangalore University, Bangalore 560 001, India

Received 30 October 2014; revised and accepted 25 March 2015

The kinetics and mechanism of oxidation of metformin hydrochloride (MET) with sodium
N-chlorobenzenesulfonamide or chloramine B have been investigated in alkaline medium at 308 K. The reaction rate shows a first order dependence of rate each on [CAB]o and [MET]o, and an inverse-first order dependence on [OH-]. The stoichiometry of the reaction is found to be in the mole ratio of 1:1. The oxidation products are characterized as metformin N-oxide by GC-MS data. Activation parameters have been computed from the Arrhenius plot. The conjugate acid (PhSO2NHCl) is postulated as the reactive oxidizing species. The observed experimental results have been justified by a plausible reaction mechanism and the related kinetic rate law has been devised.

Keywords: Kinetics, Reaction mechanism, Oxidation, Metformin hydrochloride, Chloramine-B

 

Indian Journal of Chemistry

Vol. 54A, April 2015, pp. 489-493

 

 

Photoluminescence and theoretical study of
[1(Cd2Cl6)][2(CdCl4)][3(N,N′-dimethyl-4,4′-bipyridinium)]

Zhong-Liang Yaob, Wen-Tong Chena, c,* & Rong-Hua Hua

aInstitute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Jian Jiangxi 343009, PR China

Email: cwtqq@aliyun.com

bBiology and Chemistry Engineering Department, Fuqing Branch of Fujian Normal University, Fuqing,
Fujian 350300, PR China

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

Received 25 November 2014; revised and accepted 20 March 2015

A novel cadmium chloride-4,4-bipyridinium compound, namely [1(Cd2Cl6)][2(CdCl4)][3(N,N′-dimethyl-4,4′-bipyridinium)] (1) in which the N,N-dimethyl-4,4-bipyridinium has been prepared in situ, has been obtained through solvothermal reactions and characterized by X-ray diffraction analysis. The compound crystallizes in the Pī space group of triclinic system and contains a one-dimensional (1-D) infinite 1(Cd2Cl6) chain, CdCl42 anions and [N,N-dimethyl-4,4-bipyridinium]2+ cations. These moieties interlink together via hydrogen bonding interactions to yield a three-dimensional supramolecular framework. Photoluminescence study of (1) shows emission band in the violet region. Molecular orbital calculations support the proposal that the emission originates from the ligand-to-ligand charge-transfer (LLCT) transition.

Keywords: Photoluminescence, Cadmium, X-ray diffraction, Solvothermal method