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 3

MARCH 2016

 

CONTENTS

 

 

269

 

Structural variations and chemical bonding
in platinum complexes of Group 14 heavier tetrylene homologues (germylene to plumbylene)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Nguyen Thi Ai Nhung*, Huynh Thi Phuong Loan, Duong Tuan Quang, Tran Duc Sy &
Dang Tan Hiep

 

 

 

Equilibrium geometries of heavier tetrylene complexes
[PtCl2-{NHEMe}] possess side-on-bonded NHEMe ligands.
The order of the calculated bond dissociation energy is:
Pt-NHGe < Pt-NHSn < Pt-NHPb. EDA-NOCV results indicate that the ligand NHEMe in Pt-NHE complexes is a strong
s-donor and π-donor and the trend of the Pt-E bond strength is due to the increase in PtCl2¬NHEMe donation.

 

 

 

 

277

 

Kinetic and mechanistic study of oxidation of
1,2-propanediol by aqueous alkaline solution of
N-bromosuccinimide in the presence of aquachloro-complex of ruthenium(III) as homogeneous catalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Bharat Singh*, Sandeep Kumar Mishra &
Shipra Tripathi

 

 

 

Kinetics and mechanism of Ru(III) catalysed oxidation of 1,2-propanediol by aqueous alkaline solution of N-bromosuccinimide have been investigated in the temperature range 30-45 °C. A plausible mechanism involving attack of complex formed between NBS and Ru(III)chloride in alkaline medium on 1,2-propanediol in the slow and rate determining step is suggested. The rate law consistent with observed kinetic results is presented.

 

 

 

 

Notes

 

286

 

TX-100 reverse micelles as microreactors for alkaline hydrolysis of tris(2,2ʹ-bipyridine) iron(II) complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Arjama Kundu & Ambikesh Mahapatra*

 

 

 

Alkaline hydrolysis of tris(2,2ʹ-bipyridine)iron(II) complex with sodium hydroxide has been investigated in TX-100 reverse micelles using cyclohexane/water with hexanol as cosurfactant. In reverse micellar medium, the reaction is first order with respect to each reactant. The rate decreases as the [water]/[surfactant] molar ratio increases, but increases as surfactant concentration increases.

 

 

 

 

 

292

 

In situ chemical oxidative polymerisation for ordered conducting polythiophene nanostructures in presence of dioctyl sodium sulfosuccinate

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Anne Jose, Smitha Varghese & M Jinish Antony*

 

 

 

Polythiophenes have been synthesized by chemical oxidative polymerization of thiophene in the presence of the anionic surfactant, dioctyl sodium sulfosuccinate, with ferric chloride as the oxidant in chloroform solvent. Four probe electrical conductivity measurements of the samples reveal that the conductivity is in the range of (7.4–1.0)×10-3 S cm-1 for the surfactant doped polythiophene samples. The band gap of the polymers is in the range of 2.25–2.50 eV.

 

TOC

 

 

 

298

 

Determination of sunset yellow and tartrazine using silver and poly(L-cysteine) composite film modified glassy carbon electrode

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Youxia Tang, Yanming Wang, Gen Liu* &
Dengming Sun
*

 

 

 

Compared with bare GCE, Ag/GCE and PLC/GCE, PLC/Ag/GCE possesses better selectivity and higher electrocatalytic activity for sunset yellow and tartrazine.

 

 

Graphical Abstract

 

 

304

 

Dissociation dynamics of host-guest interaction between substituted calix[4]-arene and 4-chloronitrobenzene

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ashok Kumar*, Pratibha Sharma, Pawan Kumar Sharma, Monika Ahuja, Gergely Matisz, Laszlo Kollar & Sandor Kunsagi-Mate

 

 

 

Inclusion complexation of upper rim substituted calix[4]arene with neutral 4-chloronitrobenzene is studied by quantum-chemical and spectrophotometric measurements. The formation of stable host-guest complexes is determined using DFT/B3LYP/6-311G(d) level of theory. The p-p interaction based dissociation dynamics of the host-guest complex has been studied. In the host-guest interaction, a 1:1 complex stoichiometry is observed. The low activation energy of dissociation, obtained from the MD simulations, indicates that the complex formation equilibrium is thermodynamically controlled.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

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Indian Journal of Chemistry

Vol. 55A, March 2016, pp. 269-276

 

 

Structural variations and chemical bonding in platinum complexes of
Group 14 heavier tetrylene homologues (germylene to plumbylene)

Nguyen Thi Ai Nhunga, *, Huynh Thi Phuong Loana, Duong Tuan Quangb,
Tran Duc Syb, c & Dang Tan Hiepd

Email: nguyenainhung.hueuni@gmail.com

aDepartment of Chemistry, Hue University of Sciences−Hue University, Hue, Vietnam

bDepartment of Chemistry, Hue University of Education−Hue University, Hue, Vietnam

cDepartment of Chemistry, Quang Binh University, Dong Hoi, Vietnam

dHCMC University of Food Industry, Ho Chi Minh, Vietnam

Received 14 November 2015; revised and accepted 22 February 2016

The structures of Pt(II) complexes containing the heavier homologues of germylene, stannylene, and plumbylene [PtCl2-{NHEMe}] (Pt-NHE) with E = Ge to Pb, in which the ligand {NHEMe} retains one lone pair at the E central atom, have been computed using density functional theory calculations at the BP86 level with def2-SVP, def2-TZVPP, and TZ2P+ basis sets. The bonding of the complexes has been analyzed by charge and energy decomposition analysis methods. The results of bonding analysis show that NHEMe ligands exhibit donor-acceptor bonds with the s lone pair electrons of heavier NHEMe donated into the vacant orbital of the metal fragment, and the Pt-E bonds having PtCl2←NHEMe strong s-donation. The divalent heavier tetrylenes(II) have the same role as the divalent heavier tetrylones(0) character since the ligand can retain the two lone pairs at E atom. Currently experimental efforts are directed towards the synthesis of tetrylenes Pt(II) complexes from natural products. Hence, the results in this study will provide an insight into the properties and chemical bonding of complexes being synthesised.

Keywords: Theoretical chemistry, Density functional calculations, Bonding analysis, Carbenes, Germylenes, Stannylenes, Plumbylenes, Platinum

 

Indian Journal of Chemistry

Vol. 55A, March 2016, pp. 277-285

 

 

Kinetic and mechanistic study of oxidation of 1,2-propanediol by
aqueous alkaline solution of N-bromosuccinimide in the presence of aquachloro-complex of ruthenium(III) as homogeneous catalyst

Bharat Singh*, Sandeep Kumar Mishra & Shipra Tripathi

Department of Chemistry, University of Allahabad, Allahabad 211 002, India

Email: bschem_au@yahoo.com

Received 23 November 2015; revised and accepted 7 March 2016

Kinetics of Ru(III) catalysis in oxidation of 1,2-propanediol by N-bromosuccinimide in alkaline media has been studied in presence of mercuric acetate as bromide ions scavenger in the temperature range of 30–45 °C. The reaction follows complex kinetics, being first order with respect to both 1,2-propanediol and Ru(III). First order kinetics with respect to NBS at its lower concentrations shifts to zero order at its high concentrations. Variation of both [OH-] and [KCl] shows a positive effect on the rate of reaction. Negligible effect of addition of succinimide (reduction product of NBS) is observed, while variation of both [Hg(OAc)2] and ionic strength has no effect on rate of the reactions. Various activation parameters are calculated. The products of the reactions have been identified as acetic acid and formic acid. A suitable mechanism in conformity with the kinetic observations is discussed and rate law derived.

Keywords: Kinetics, Reaction mechanism, Oxidation, 1,2-Propanediol, N-Bromosuccinimide, Ruthenium

 

 

Indian Journal of Chemistry

Vol. 55A, March 2016, pp. 286-291

 

 

TX-100 reverse micelles as microreactors for alkaline hydrolysis of
tris(2,2ʹ-bipyridine) iron(II) complex

Arjama Kundu & Ambikesh Mahapatra*

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

Email: ambikeshju@gmail.com; amahapatra@chemistry.jdvu.ac.in

Received 2 December 2015; accepted 29 February 2016

Alkaline hydrolysis reaction of tris(2,2ʹ-bipyridine)iron(II) complex with sodium hydroxide has been investigated in TX-100 reverse micelles using cyclohexane/water with hexanol as cosurfactant by spectrophotometric method. In reverse micellar medium, the reaction is first order with respect to each reactant. The effects of water pool size and surfactant concentration are investigated. The rate decreases as the [water]/[surfactant] molar ratio (W) increases, but increases as surfactant concentration increases. Effect of both W and surfactant concentration are prominent at lower regions of W. The results are explained by considering the occurrence of two reactions at a measurable speed in reverse micellar medium, i.e., aqueous dissociation and alkaline hydrolysis reactions. Both these reactions in the reverse micellar medium are catalyzed. In the water pool, properties of water are such that at lower W, dissociation reaction is favorable, whereas at higher W, hydrolysis is favorable. Experimental results also conclude that dissociation occurs mainly at the interface and hydrolysis in the cavity of the water pool.

Keywords: Hydrolysis, Alkaline hydrolysis, Surfactants, Reverse micelles, Microreactors, Dissociation,
Water pools, Micropolarity

 

Indian Journal of Chemistry

Vol. 55A, March 2016, pp. 292-297

 

 

In situ chemical oxidative polymerisation for ordered conducting polythiophene nanostructures in presence of dioctyl sodium sulfosuccinate

M Anne Josea, Smitha Vargheseb & M Jinish Antonyb, *

aDepartment of Physics, Little Flower College, Affiliated to University of Calicut, Guruvayoor, 680 103, Kerala, India

bResearch and PG Department of Chemistry, Centre for Sustainable Chemistry, St. Thomas College (Autonomous), Affiliated to University of Calicut, Thrissur, 680 001, Kerala, India

Email: jinish06@yahoo.co.in

Received 9 March 2015; revised and accepted 4 March 2016

Polythiophenes (PTs) have been synthesized by chemical oxidative polymerization of thiophene in the presence of an anionic surfactant dioctyl sodium sulfosuccinate (AOT) using ferric chloride as an oxidant in chloroform solvent. Different monomer/surfactant ratios have been employed to study the effect of surfactant on synthesis and properties of polythiophenes. The PTs have been characterized by FT-IR spectroscopy,
wide-angle powder X-ray diffraction and elemental analysis. The properties of PTs prepared using AOT surfactant have been compared with those of PT synthesized without surfactant. Four probe electrical conductivity measurements of the samples reveal that the conductivity is in the range of (7.4–1.0)×10-3 S cm-1 for AOT doped polythiophene samples. The band gap of the polymers determined from diffuse reflectance spectroscopy is in the range of 2.25–2.50 eV. Scanning electron microscopic images of the samples exhibited spherical nanoparticle morphology with size in the range of 800 ± 50 nm.

Keywords: Polymerisation, Chemical oxidative polymerisation, Polymers, Conducting polymers, Polythiophenes, Anionic surfactants

 

 

 

Indian Journal of Chemistry

Vol. 55A, March 2016, pp. 298-303

 

 

Determination of sunset yellow and tartrazine using silver and
poly(L-cysteine)
c
omposite film modified glassy carbon electrode

Youxia Tang, Yanming Wang, Gen Liu* & Dengming Sun*

School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, PR China

Email: liugen7084@126.com (GL); sundengming@126.com (DS)

Received 26 May 2015; revised and accepted 11 February 2016

Silver and poly(L-cysteine) composite film modified glassy carbon electrode (PLC/Ag/GCE) has been fabricated via cyclic voltammetry and used for investigation of the electrochemical behavior of sunset yellow (SY) and tartrazine (TT). A pair of anodic peak at 0.760 V (vs. Ag/AgCl) and cathodic peak at 0.701 V
(vs. Ag/AgCl) for SY and an anodic peak at 1.013 V (vs. Ag/AgCl) of TT are observed in pH 4.5 phosphate buffer solution. Based on the two well-resolved anodic peaks of SY and TT, a novel electrochemical method has been successfully developed for simultaneous determination of SY and TT using differential pulse voltammetry. Under the optimized experimental conditions, the linear range for the determination of SY and TT are 5.00×10-7 –3.00×10-4 mol L-1 and 7.50×10-7–7.50×10-4 mol L-1, respectively with detection limits of 7.50×10-8 mol L-1 and 2.50×10-7 mol L-1, respectively. The proposed method has been applied for simultaneous determination SY and TT in beverage with satisfactory results.

Keywords: Analytical chemistry, Electroanalytical methods, Electrodes, Modified electrodes, Films, Composite films, Sunset yellow, Tartrazine

 

Indian Journal of Chemistry

Vol. 55A, March 2016, pp. 304-308

 

 

Dissociation dynamics of host-guest interaction between
substituted calix[4]-arene and 4-chloronitrobenzene

Ashok Kumara,*, Pratibha Sharmaa, Pawan Kumar Sharmaa, Monika Ahuja a, Gergely Matiszb,
Laszlo Kollarc & Sandor Kunsagi-Mateb

aSchool of Chemical Sciences, Devi Ahilya University, Takshashila Campus, Indore 452 001, India

bDepartment of General and Physical Chemistry, University of Pecs, Ifjusag 6, H-7624 Pecs, Hungary

cDepartment of Inorganic Chemistry, University of Pécs, Ifjúság 6, H-7624, Pécs, Hungary

Email: drashoksharma2001@yahoo.com

Received 11 July 2015; accepted 3 March 2016

The inclusion complexation of upper rim substituted calix[4]arene with neutral 4-chloronitrobenzene has been studied by quantum-chemical and spectrophotometric measurements. The effect of varying temperature on the formation versus dissociation of the host-guest complex has been investigated. The formation of stable
host-guest complexes is determined using DFT/B3LYP/6-311G(d) level of theory. The
p-p interaction based dissociation dynamics of the host-guest complex has been studied. In the host-guest interaction, a 1:1 complex stoichiometry is observed. The low activation energy of dissociation, obtained from the MD simulations, indicates that the complex formation equilibrium is thermodynamically controlled.

Keywords: Supramolecular chemistry, Host-Guest interactions, Density functional calculations, Calix[4]arene, Molecular dynamics,