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 55A

NUMBER 8

AUGUST 2016

 

CONTENTS

 

 

919

 

Synthesis of quinolines from glycerol over tungstic acid functionalized mesoporous KIT-6 catalyst in aqueous medium

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

V Udayakumar & A Pandurangan*

 

 

 

With mesoporous tungstic acid functionalized KIT-6 nanoparticles as catalyst in the Skraup synthesis of glycerol, aniline and water as solvent, the target quinoline and its derivatives are obtained in up to 89% yield with complete conversion of glycerol (100%) under the reaction conditions of 200 oC for 3 h. The para substituted anilines with electron-rich groups afford higher yields as compared to those with electron-deficient groups.

 

 

 

 

 

929

 

Ruthenium carbonyl complex bearing thioether containing Schiff base ligand: Structure, electrochemistry and catalytic activity

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sujan Biswas, Puspendu Roy, Deblina Sarkar & Tapan Kumar Mondal*

 

 

 

Ruthenium(II) carbonyl complex, cis-(CO)-trans-(Cl)-[Ru(CO)2(L)Cl2] (L = 2-(methylthio)-N-((pyridine-2-yl)methylene)-benzenamine), has been synthesized. The pseudo-octahedral geometry of the complex has been confirmed by single crystal
X-ray diffraction data. Cyclic voltammetry exhibits irreversible Ru(II)/Ru(III) oxidation along with irreversible ligand based reduction; the redox properties are supported by
DFT calculations. The electronic spectrum of the complex has been interpreted by spin allowed electronic transitions computed by TDDFT method and is in good agreement with the experimental spectrum. Quantum yield calculations and lifetime measurement emission show quantum yield of the complex to be 0.027, while the emission lifetime of the complex is found to be 3.93 ns. The ruthenium(II) complex efficiently catalyzes the oxidation of alcohols (77-84%) in presence of N-methylmorpholine-N-oxide.

 

 

 

 

 

 

938

 

Structure and reactivity of di-n-butyltin(IV) derivative of chlordiazepoxide based on electronic structure calculations

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sandeep Pokharia*, Rachana Joshi, Mamta Pokharia, Swatantra Kumar Yadav & Hirdyesh Mishra

 

 

 

A DFT study on n-Bu2SnL2 (L = monoanion of chlordiazepoxide) calculates a distorted tetrahedral geometry around the central Sn atom, and different degrees of interaction for the two chlordiazepoxide units with the di-n-butyltin(IV) moiety.

 



 

Notes

 

950

 

Bifunctional organocatalysts for the synthesis of jasminaldehyde and their derivatives

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Venkata Subba Rao Ganga, Sayed H R Abdi*, Rukhsana I Kureshy, Noor-ul H Khan &
Hari C Bajaj
*

 

 

 

Jasminaldehyde is synthesized by cross-aldol condensation
of benzaldehyde with 1-heptanal under solvent free condition
and in presence of L-proline in combination with benzoic
acid. Under the optimized reaction conditions, jasminaldehyde
is formed with 96% selectivity in one hour with the desired
arylaldehyde:1-alkanaldehyde ratio as low as 2:1 under controlled addition of 1-alkanaldehyde.

 

 

 

 

956

 

Catalysis by AOT reverse micelles - Kinetics of aquation of bis(2,4,6–tripyridyl-s-triazine)iron(II) and acid hydrolysis of 2,2′,6,6′′ terpyridyl iron(II) in the presence of AOT/heptane

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Padma, P Shyamala* & P V Subba Rao

 

 

 

The aquation of {Fe(tptz)2}2+ is very slow and incomplete in aqueous medium while the reaction is accelerated markedly in AOT reverse micelles. The catalysis observed in reverse micelles is due to the special properties of water pool-like high nucleophilicity of water and the low dielectric constant.

 

 

GA edited 1

 

 

 

 

962

 

Structural features and photocatalytic performance of H3Nb6O195-  intercalated Ni-Ti-LDHs

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hong Liu*, Wei Gao, Xianying Liu & Jie He

 

 

 

Ni-Ti-layered double hydroxides have been synthesized by
co-precipitation and modification by H3Nb6O195- polyanion and characterized by PXRD, SEM, TEM, FT-IR and UV-vis DRS data. The photocatalytic performance has been evaluated by oxidation of ethyl mercaptan as a probe molecule. The results show that there is an obvious interaction between H3Nb6O195- and the laminates, and the interlayer H3Nb6O195- polyanion enhances the adsorption and photocatalytic performance of Ni-Ti-LDHs for oxidation of ethyl mercaptan.

 

 

 

967

 

 Guide to Authors

 

 

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 


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Indian Journal of Chemistry

Vol. 55A, August 2016, pp. 919-928

 

 

Synthesis of quinolines from glycerol over tungstic acid functionalized

mesoporous KIT-6 catalyst in aqueous medium

V Udayakumar & A Pandurangan*

Department of Chemistry, Anna University, Guindy, Chennai 600 025, India

Email: pandurangan_a@yahoo.com

Received 10 June 2016; accepted 28 July 2016

Mesoporous tungstic acid functionalized KIT-6 has been synthesized through a condensation of
(3-chloropropyl) triethoxysilane and Si-KIT-6 followed by substitution of chloromethylation functionalized KIT-6 by sodium tungstate dihydrate. The synthesized tungstic acid functionalized KIT-6 (W-KIT-6) was characterized by low and wide angle X-ray diffraction analysis (XRD), N
2 adsorption-desorption isotherm, scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), NH3-temperature programmed desorption (NH3-TPD), 13C CP/MAS NMR spectrum and FT-IR analysis. The functionalized KIT-6 posses surface area of 663 m2/g with corresponding pore size 6.3 nm and pore volume 0.65 cm3/g. The catalytic activity of W-KIT-6 nanoparticles evaluated in the Skraup synthesis of quinoline and its derivatives using water as solvent, the results show the target compound was obtained as 89% yield with complete conversion of glycerol (100%) under the reaction conditions of 200 oC for 3 h. The catalyst has been recycled for five times without significant loss in catalytic activity.

Keywords: Catalysts, Mesoporous catalysts, Functionalized catalysts, Skraup synthesis, W/KIT-6, Quinoline, Glycerol

 

Indian Journal of Chemistry

Vol. 55A, August 2016, pp. 929-937

 

 

Ruthenium carbonyl complex bearing thioether containing Schiff base ligand: Structure, electrochemistry and catalytic activity

Sujan Biswas, Puspendu Roy, Deblina Sarkar & Tapan Kumar Mondal*

Inorganic Chemistry Section, Department of Chemistry, Jadavpur University, Kolkata 700 032, India

Email: tkmondal@chemistry.jdvu.ac.in

Received 13 January 2016; revised and accepted 22 July 2016

New ruthenium(II) carbonyl complex, cis-(CO)-trans-(Cl)-[Ru(CO)2(L)Cl2] (1) (L = 2-(methylthio)-
N-((pyridine-2-yl) methylene)benzenamine) has been synthesized and characterized by several spectroscopic techniques. The geometry of the complex has been confirmed by single crystal X-ray structure. Cyclic voltammogram of (1) exhibits irreversible Ru(II)/Ru(III) oxidation and ligand based reduction. The electronic structure, redox properties, absorption and emission properties of the complex have been interpreted by DFT and TDDFT calculations. The complex efficiently catalyzes the oxidation of alcohols in presence of
N-methylmorpholine-N-oxide.

Keywords: Coordination chemistry, Carbonyl complexes, Schiff bases, Oxidation, Alcohol oxidation, Photophysical properties, Electrochemistry, X-ray structure, Ruthenium

 

 

 

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 55A, August 2016, pp. 938-949

 

 

Structure and reactivity of di-n-butyltin(IV) derivative of chlordiazepoxide based on electronic structure calculations

Sandeep Pokhariaa, *, Rachana Joshia, Mamta Pokhariaa, Swatantra Kumar Yadavb & Hirdyesh Mishrab

aOrganometallics and Molecular Modelling Group, Chemistry Section, Mahila Mahavidyalaya,
Banaras Hindu University, Varanasi 221 005, India

Email: sandeepp@bhu.ac.in

bPhysics Section, Mahila Mahavidyalaya Banaras Hindu University, Varanasi 221 005, India

Received 28 December 2015; revised and accepted 27 July 2016

Density functional theory calculations in electronic structure studies of n-Bu2SnL2 (where L is the monoanion of chlordiazepoxide (LH), a benzodiazepine derivative with hypnotic action) have been reported using the Gaussian09 software. The molecular geometries of LH and tetrahedral n-Bu2SnL2 have been optimized at B3LYP/6-31G(d,p) and B3LYP/ 6-31G(d,p)/Def2-SVP(Sn) level of theory, respectively. Harmonic vibrational frequencies are computed at the same level of theory to find the true potential energy surface minima. The effect of functional, basis set and computational cost is analyzed. The various geometrical and thermochemical parameters have been obtained in gas phase and in the solvent. The atomic charges at all the atoms are calculated using Mulliken population analysis, Hirshfeld population analysis and natural population analysis. The charge distribution within the studied complex is explained on the basis of molecular electrostatic potential maps,and conceptual-DFT based global reactivity descriptors using the finite difference approximation method. The calculated parameters suggest a distorted tetrahedral geometry around the central Sn atom. The calculated Sn−O bond lengths reveals different degree of interaction of two chlordiazepoxide units with the di-n-butyltin(IV) moiety. Among the atoms coordinated to the central Sn atom, oxygen from one LH unit is nucleophilic, whereas the second oxygen atom from the other LH unit is electrophilic in nature. The results provide an insight into the efficacy of computational methods in understanding the structure and reactivity of organotin(IV) derivatives of hetero donor atoms.

Keywords: Theoretical chemistry, Density functional calculations, Electronic structures, Global reactivity descriptors, Organotin compounds, Tin, Chlordiazepoxide

 

Indian Journal of Chemistry

Vol. 55A, August 2016, pp. 950-955

 

 

Bifunctional organocatalysts for the synthesis of jasminaldehyde
and their derivatives

Venkata Subba Rao Gangaa, b, Sayed H R Abdia, b, *,Rukhsana I Kureshya, b,
Noor-ul H Khana, b & Hari C Bajaja, b, *

aInorganic Materials and Catalysis Division,CSIR-Central Salt and Marine Chemicals Research Institute
(CSIR-CSMCRI), Bhavnagar 364 002, Gujarat, India

bAcademy of Scientific and Innovative Research, CSIR-Central Salt and Marine Chemicals Research Institute
(CSIR-CSMCRI), Bhavnagar 364 002, Gujarat, India

Email: shrabdi@csmcri.org (SHRA); hcbajaj@csmcri.org (HCB)

Received 8 April 2016; revised and accepted 29 July 2016

L-Proline in the presence of benzoic acid is found to be an effective catalytic system for the cross-aldol condensation of benzaldehyde with 1-heptanal under solvent free condition amongst the several amino acids screened for this reaction. Under the optimized reaction conditions, the desired product (e.g. jasminaldehyde) is formed up to 96% selectivity in one hour using the desired arylaldehyde: 1-alkanaldehyde ratio as low as 2:1 under controlled addition of 1-alkanaldehyde.

Keywords: Catalysis, Organocatalysts, Bifunctional organocatalysts,Cross-aldol condensation Jasminaldehyde, Heptanal

Indian Journal of Chemistry

Vol. 55A, August 2016, pp. 956-961

 

 

Catalysis by AOT reverse micelles Kinetics of aquation of bis(2,4,6–tripyridyls-triazine)iron(II) and acid hydrolysis of 2,2,6,6′′terpyridyl iron(II) in the presenceof AOT/heptane

M Padmaa, P Shyamalaa, * & P V Subba Raob

aDepartment of Physical Chemistry, Andhra University, Visakhapatnam 530 003, India

Email: shyamalapulipaka@rediffmail.com

bDepartment of Chemistry, G VP PG College of Science, Visakhapatnam 530 003, India

Received 14 April 2016; revised and accepted 26 July 2016

The kinetic study of the aquation of bis(2,4,6–tripyridyl-striazine) iron(II), {Fe(tptz)2}2+ and acid hydrolysis of 2,2,6,6′′ terpyridyl iron(II), {Fe(terpy)2}2+ have been carried out in the presence of water pools of AOT/heptane reverse micelles. The aquation of {Fe(tptz)2}2+ is markedly accelerated in the presence of AOT/heptane reverse micelles compared to aqueous medium. The significant increase in rate is attributed to the special properties of the water pool-like high nucleophilicity of water, low dielectric constant and favourable partitioning of tptz ligand into the organic phase. The rate of the reaction increases with increase in [H2O] at constant [AOT] and decreases linearly with increase in [AOT] at constant [H2O]. The dependence of the aquation rate on water concentration has been used in elucidating the role of water in the rate determining step. In the acid hydrolysis of {Fe(terpy)2}2+ the reaction proceeds with a rate constant k= 11.2×10-4 s-1 in the presence of AOT/heptanes while the reaction is extremely slow and incomplete under identical conditions in aqueous medium.Higher rate observed in reverse micelles is attributed to low dielectric conditions in the water pool. The study has been carried out at different W values and at different surfactant concentrations (W = [H2O]/[surfactant]). The effect of surfactant concentration has been explained on the basis of Berezin pseudo phase model.

Keywords: Micelles, Reverse micelles, Aquation, Hydrolysis, Acid hydrolysis, Surfactants Kinetics,
Water pools, Iron

 

Indian Journal of Chemistry

Vol. 55A, August 2016, pp. 962-966

 

 

Structural features and photocatalytic performance of H3Nb6O195-intercalated Ni-Ti-LDHs

Hong Liua, *, Wei Gaob, Xianying Liuc & Jie Heb

aDepartment of Chemical Engineering, Huainan Union University, Huainan, 232038, PR China

Email: liuhongxw@126.com

bSchool of Chemical Engineering, Anhui University of Science and Technology, Huainan, 232001, PR China

cThe Second Hospital of Jilin University, Clinical Skills Training Center, Changchun, 130041 PR China

Received 8 August 2015; revised and accepted 1 August 2016

Ni-Ti-layered double hydroxides (Ni-Ti-LDHs) have been synthesized by co-precipitation and modified by H3Nb6O195- polyanion. The as-prepared samples have been characterized by power X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared and UV-visible diffuse reflectance spectroscopy. The photocatalytic performance has been evaluated by oxidation of ethyl mercaptan as a probe molecule. The results show that there is an obvious interaction between H3Nb6O195 and laminates, and interlayer H3Nb6O195 polyanion enhances the adsorption and photocatalytic performance of Ni-Ti-LDHs for oxidation of ethyl mercaptan.

Keywords: Photocatalysis, Photocatalytic oxidation, Oxidation, Layered double hydroxides, Nickel, Titanium, Polyanion, Ion-exchange, Ethyl mercaptan