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 5

MAY 2015

 

CONTENTS

 

 

581

 

Synthesis, structure and reactivity of triosmium clusters derived from the reactions of [Os3(CO)10(µ-dppm)] and [(µ-H)Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}] with tris(4-fluorophenyl)phosphine and tris(cyanoethyl)phosphine

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Abdur R Miah, Subas Rajbangshi, Kamal Hossain, Tasneem A Siddiquee & Shariff E Kabir*

 

 

 

The new clusters, [Os3(CO)9(µ-dppm)(PR3)] (R = (4-FC6H4); (CH2CH2CN)3), upon thermolysis in refluxing toluene
affords the electron-deficient compounds [(µ-H)Os3(CO)73-Ph2PCH2PPh(C6H4)}{PR3)}] (R = (4-FC6H4); (CH2CH2CN)3).

 

 

 

 

588

 

Synthesis, characterization and applications of vinyl functionalized N-heterocyclic carbene supported ruthenium(II) derivatives

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Paladugu Suresh, Venkatesan Munisamy &
Ganesan Prabusankar
*

 

 

 

New pre-NHC precursors featuring a short π donor functional group attached with carbene and new vinyl functionalized NHC supported ruthenium derivatives have been synthesized from the corresponding silver carbene precursors. Spectral studies of the NHC metal derivatives show the presence of vinyl π electron delocalization with five-membered NHC ring, and the absence of
π coordination towards the ruthenium centre.

 

 

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596

 

Supramolecular interactions between a diamine-diamide ligand and anions, trigonal planar NO3- and spherical Cl-: Multiple hydrogen bond cooperativity through water molecules

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jyothi Sunkari, Shashank Kundha,
Raghava Rao Gundapaneni, Anjali Reddy,
Someshwar Pola, Sreedhar Kodumuru &
Jagannatha Swamy Sreedasyam
*

 

 

 

The diamine-diamide ligand, N,N'-propane-1,3-diyl-bis-(2-aminobenzamide), forms anion complexes of the type, PBABH22+(NO3)2-(H2O)2 and PBABH22+(Cl)2-(H2O)2 with primary and secondary H-bonds.

 

 

 

 

607

 

Layered double hydroxides based on different cations as catalysts for synthesis of poly(1, 5-pentadiol) carbonate diols

 

 

 

 

 

 

 

 

 

 

Liping Wang*, Fan Wang & Linxiao Xu

 

 

 

Layered double hydroxides based on different metal cations have been prepared by co-precipitation method and used as catalysts for transesterification between diphenyl carbonate and 1, 5-pentadiol to poly(1,5-pentadiol) carbonate diols. Zn-Al-CO3 LDH and
Mg-Al-CO3 LDH are found to be the most effective catalysts.

 

 

 

 

613

 

Solar light assisted photocatalytic mineralization of an azo dye, sunset yellow by using CAC/TiO2 composite catalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

D Rajamanickam & M Shanthi*

 

 

 

 

 

619

 

Ab initio and DFT studies on ionization of octopamine and 6-aminopenicillanic acid in aqueous solution

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Farhoush Kiani, Mehran Abbaszadeh,
Mohammad Pousti & Fardad Koohyar
*

 

 

 

Calculated structures of octapamine and 6-APA in water at
298.15 K are investigated using the Tomasi’s method at the B3LYP/6-31+G(d) level of theory. Comparison of the calculated results with experimental values in terms of pKa values shows reasonable agreement between the two.

 

 

 

 

 

Notes

 

627

 

An efficient cloud point extraction method for the separation of congo red using Triton X-100 in the presence additives

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Nilesh Dharaiya*, Arpan Parmar & Pratap Bahadur

 

 

 

An efficient, feasible and green method for removal of dyes has been developed based on cloud point extraction. A small concentration of long chain glycol ether (ethylene glycol monohexyl ether) improves the efficiency of Triton X-100 for complete removal of congo red from aqueous media over a wide range of temperature.

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 581-587

 

 

Synthesis, structure and reactivity of triosmium clusters derived from the reactions of [Os3(CO)10(µ-dppm)] and [(µ-H)Os3(CO)8{µ3-Ph2PCH2P(Ph)C6H4}] with tris(4-fluorophenyl)phosphine and tris(cyanoethyl)phosphine

Abdur R Miaha, Subas Rajbangshia, Kamal Hossaina, Tasneem A Siddiqueeb & Shariff E Kabira,*

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

Email: skabir_ju@yahoo.com

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

Received 4 January 2015; revised and accepted 27 April 2015

The reactions of [Os3(CO)10(µ-dppm)] (1) with tris(4-fluorophenyl)phosphine, P(4-FC6H4)3, and tris(cyanoethyl)
phosphine, P(CH2CH2CN)3, in the presence of Me3NO in refluxing dichloromethane give the mono-substituted
clusters [Os3(CO)9(µ-dppm){P(4-FC6H4)3)}] (2) and [Os3(CO)9(µ-dppm){P(CH2CH2CN)3)}] (3), respectively, in which the phosphine is bound to the non-dppm-substituted osmium center. The 46-electron compound
[(µ-H)Os3(CO)8-{µ3-Ph2PCH2P(Ph)C6H4}] (6) reacts with an excess of P(4-FC6H4)3 and P(CH2CH2CN)3 at ambient temperature to yield (2) and (3), respectively. Heating (2) or (3) in refluxing toluene at 110 oC afforded the electron-deficient clusters [(µ-H)-Os3(CO)73-Ph2PCH2PPh(C6H4)}{P(4-FC6H4)3)}] (4) and [(µ-H)Os3(CO)73-Ph2PCH2PPh(C6H4)}{P(CH2CH2CN)3}] (5) resulting from C-H bond scission of the coordinated dppm and metal hydride bond formation. The molecular structures of (2), (3) and (4) have been determined by single- crystal X-ray diffraction studies.

Keywords: Organometallic compounds, Triosmium clusters, Phosphines, Substitution reaction, Orthometalation, X-ray structures

 

Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 588-595

 

 

Synthesis, characterization and applications of vinyl functionalized
N-heterocyclic carbene supported ruthenium(II) derivatives

Paladugu Suresh, Venkatesan Munisamy & Ganesan Prabusankar*

Department of Chemistry, Indian Institute of Technology Hyderabad, ODF Campus,
Yeddumailaram 502 205 Telangana,
India

Email: prabu@iith.ac.in

Received 11 March 2015; revised and accepted 23 April 2015

New ruthenium(II) N-heterocyclic carbene complexes of the general formula [ArCH2(VIm)RuCl2(p-cymene)]
(VIm = vinylimidazole; Ar = mesitylene (5) or napthalene (6)) are obtained from the transmetallation reaction between [MesCH2(VIm)AgBr] (Mes = mesitylene (3)) or [NpCH2(VIm)AgCl]  (Np = napthalene (4)) and
[(p-cymene)RuCl2]2. The silver carbene complexes (3) and (4) are synthesized from the direct reaction between the corresponding π-functionalized imidazolium salts, [MesCH2(VIm)Br] (1) or [NpCH2(VIm)Cl]  (2), with silver oxide in good yield. The compounds (1), (2), (5) and (6) are characterized by elemental analysis, FT-IR and multinuclear (1H and 13C) NMR spectroscopy. Furthermore, ligand (1) is characterized by single crystal X-ray diffraction technique. The coordination mode and possible olefin-Ru π-interaction in (5) and (6) are investigated. The complexes (5) and (6) are stable and soluble in dichloromethane and chloroform.Compounds (5) and (6) are catalytically active towards the hydrogen transfer reactions.

Keywords: Coordination chemistry, Metal-olefin interactions, Transmetallation, Hydrogenation,
Heterocyclic compounds, Carbenes, N-Heterocyclic carbenes, Carbonyls,
Silver, Ruthenium

 

Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 596-606

 

 

Supramolecular interactions between a diamine-diamide ligand and anions, trigonal planar NO3- and spherical Cl-: Multiple hydrogen bond
cooperativity through water molecules

Jyothi Sunkari, Shashank Kundha, Raghava Rao Gundapaneni, Anjali Reddy, Someshwar Pola,
Sreedhar Kodumuru & Jagannatha Swamy Sreedasyam*

Department of Chemistry, Kakatiya University, Warangal 506 009, India

Email: sj_swamy@yahoo.com

Received 11 September 2014; revised and accepted 27 April 2015

Supramolecular interactions between NO3- and Cl- and the diamine-diamide ligand, N,N'-propane-1,3-diyl-bis-
(2-aminobenzamide) (PBAB), are reported. The diprotonated PBAB interacts with anions, trigonal planar NO3- and spherical Cl-, resulting in H-bonded supramolecular entities. Formation of the anion complexes is established by the
pH-potentiometric and electronic spectral studies in solution. Comparison of the mass, IR and 1H-NMR spectra of the free ligand with the salts of NO3- and Cl- confirm the formation of the complexes. Single crystal X-ray diffraction investigations of the solids reveal the stoichiometry, structures of the complexes and rich variety of hydrogen bond motifs involving the protonated amine (–NH3+), amide –NH, alkyl and aryl –C-H, H2O and anions and
p-p interactions between adjacent cations. Unlike the free ligand (triclinic, P-1) and the chloride ion adduct (monoclinic, P21/c), the nitrate salt is found to be centrosymmetric (monoclinic, C2/c).

Keywords: Supramolecular interactions, H-bonding, Diamine-diamide ligands, Anion complexes, Nitrates, Chlorides

 

Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 607-612

 

 

Layered double hydroxides based on different cations as catalysts for
synthesis of poly(1, 5-pentadiol) carbonate diols

Liping Wang*, Fan Wang & Linxiao Xu

College of Chemistry and Chemical Engineering, Qujing Normal University, PR China

Email: wanglp_csu@163.com

Received 13 October 2014; revised and accepted 6 April 2015

Layered double hydroxides (LDHs) based on different metal cations have been prepared by co-precipitation method and characterized with X-ray diffraction and Fourier transform infrared spectroscopy. The sample LDHs have been used as catalysts for transesterification between diphenyl carbonate (DPC) and 1, 5-pentadiol (1, 5-PD) to poly(1,5-pentadiol) carbonate diols. The results show that Zn-Al-CO3 LDH and Mg-Al-CO3 LDH are the most effective catalysts for the transesterification between DPC and 1,5-PD. Taking Zn-Al-CO3 LDH as an example, the effect of the layered structure of LDHs on the transesterification has been investigated. The results show that the stability of layered structure is an important factor that influences the catalytic activity of LDHs.

Keywords: Layered double hydroxides, Diphenyl carbonate, Transesterification, Pentadiol, Polycarbonate diols, Diols

 

Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 613-618

 

 

Solar light assisted photocatalytic mineralization of an azo dye, sunset yellow by using CAC/TiO2 composite catalyst

D Rajamanickam & M Shanthi*

Photocatalysis Laboratory, Department of Chemistry, Annamalai University, Annamalainagar 608 002,
Tamil Nadu, India

Email: shanthimsm@gmail.com

Received 25 June 2014; revised and accepted 13 April 2015

CAC/TiO2 composite photocatalysts have been prepared by sol gel method and photocatalytic activity investigated for the degradation of sunset yellow in aqueous solution using solar light. CAC/TiO2 is found to be more efficient than TiO2 and TiO2-P25 at pH 7 for the mineralization of the dye. Effects of operational parameters such as the amount of photocatalyst, dye concentration and initial pH on photomineralization of SY have been analyzed. The degradation is strongly enhanced in the presence of electron acceptors such as oxone, KIO4 and KBrO3. Mineralization of the dye has been confirmed by COD measurments. The proposed mechanism of degradation by CAC/TiO2 shows a pseudo-first order. The catalyst is found to be reusable up to the fourth cycle.

Keywords: Photocatalysis, Sol gel method, Degradation, Dye degradation, Solar light, Titiania

 

Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 619-626

 

 

Ab initio and DFT studies on ionization of octopamine and
6-aminopenicillanic acid in aqueous solution

Farhoush Kiani a, Mehran Abbaszadeha, Mohammad Poustia & Fardad Koohyara, *

a Department of Chemistry, Faculty of Science, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran
Email: fardadkoohyar@yahoo.com

Received 2 March 2015; revised and accepted 15 April 2015

The existing quantum chemical methods to accurately predict pKa and to determine the trade-off between accuracy and computational cost have been evaluated by ab initio and density functional theory with the B3LYP functional and 6-31+G(d) basis sets and polarizable continuum solvation model. The calculated free energies for determination of pKa values, and intermolecular hydrogen bonds in aqueous solutions of octopamine and
6-aminopenicillanic acid have been computed. This study shows that there is reasonable agreement between the theoretically calculated pKa values and the experimentally determined pKa values for the acid-base reactions obtained by potentiometric and spectrophotometric methods reported in the literature.

Keywords: Theoretical chemistry, Ab initio calculations, Density functional calculations,
Acid dissociation constant, 6-Aminopenicillanic acid, Octopamine

 

 

 

Indian Journal of Chemistry

Vol. 54A, May 2015, pp. 627-632

 

 

An efficient cloud point extraction method for the separation of congo red
using Triton X-100
in the presence additives

Nilesh Dharaiya*, Arpan Parmar & Pratap Bahadur

Department of Chemistry, Veer Narmad South Gujarat University, Surat 395 007, India

Email: nilesh.dharaiya@yahoo.com/ pbahadur2002@yahoo.com (PB)

Received 3 December 2014; revised and accepted 29 April 2015

A new approach to improve the cloud point extraction of congo red (a hazardous anionic azo dye) from aqueous solution using Triton X-100 surfactant is reported. The interaction of congo red with Triton X-100 during micellar solubilization has also been investigated by visible absorption spectral studies. The optimum conditions for surfactant concentration, additives (salts, glycols and their ethers) concentration, temperature and pH have been determined to achieve higher extraction. Among the various glycol ethers studied, ethylene glycol monohexyl ether shows the most efficient extraction of the dye even at ambient temperature, with almost complete removal of the dye from aqueous solution.

Keywords: Cloud point extraction, Surfactants, Dyes, Azo dyes, Congo red, Triton X-100, Glycol ethers