Indian Journal of Chemistry

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

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VOLUME 47A

NUMBER 5

May 2008

CONTENTS

 

643

 

Synthesis, structure, DNA-binding and photocleavage activity of a binuclear copper(II) complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ashis K Patra, Tarkeshwar Gupta, Sovan Roy & Akhil R Chakravarty*

 

 

 

Binuclear copper(II) complex [CuL]2(NO3)2 (1) has been prepared and structurally characterized by X-ray crystallography. Complex 1 shows a Cu-S bond in a CuNO3S coordination geometry and displays DNA binding and photocleavage activity.

 

 

 

 

 

 

650

 

Synthesis, characterization and electrical conductivities of mixed-ligand (N, S/Se) heterobimetallic coordination polymers and their
I2-doped products

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Nanhai Singh* & Akhilesh Prasad

 

 

 

New mixed-ligand heterometallic coordination polymers of the type [MM΄(Et2dtc)2(bzta)2], [MM˘(XCN)2(Et2dtc)2], [Cu2Hg(SCN)2(bzta)2] and [CuAg(SCN)(bzta)] [M = Ni(II) or Cu(II); M˘ = Ni(II), Zn(II), Cd(II), Hg(II), Pb(II) or 2Ag(I); 
X = S or Se; bzta- = benzothiazole-2-thiolate (C6H4NSCS-); Et2dtc- = diethyldithiocarbamate {(C2H5)2NCS2-}] have been prepared and characterized.

 

 

 

 

 

657

 

Reactions of electron-deficient benzoquinoline triosmium cluster [(m-H)Os3(CO)9(m3-h2-C13H8N)] with diazomethane

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Shariff E Kabir*, Mohammad A Rahman,
Md.
Nazim Uddin & Noorjahan Begum

 

 

 

The synthesis and thermal transformation of the methylene inserted benzoquinoline triosmium compound
[(
m-H)2Os3(CO)9{m3-h2-CH(C13H8N)}]  are described.

 

663

 

Synthesis of carbon nanotubes over transition metal ions supported on Al(OH)3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

H Kathyayini, K Vijayakumar Reddy, J B Nagy &
N Nagaraju*

 

 

 

Production of carbon nanotubes on bi-metallic (Fe/Co, Co/Ni, Fe/Ni, Fe/Mo, Co/Mo, Ni/Mo) and trimetallic (Fe/Co/Mo, Co/Ni/Mo, Fe/Ni/Mo) catalysts supported on Al(OH)3 by catalytic chemical vapor deposition is reported.

 

 

 

669

 

Correlation analysis of reactivity in the oxidation of substituted benzyl alcohols by morpholinium chlorochromate

 

 

 

 

Neelam Soni, Vandana Tiwari & Vinita Sharma*

 

 

 

Oxidation of benzyl alcohol and some ortho-, meta- and para-monosubstituted ones by morpholinium chlorochromate in dimethyl sulphoxide leads to the formation of corresponding benzaldehydes. The reaction is first order each in both morpholinium chlorochromate and the alcohol.

 

     ArCH2OH    +   CrO2ClOMH       ľ® 

                                            ArCHO    +     (HO)2CrClOMH

 

 

677

 

Studies on the configuration and structural stability of cyanides Fe(CN)n (n=1-4)

 

 

 

Xue-jun Sun, Wen-juan Wang, Zheng-yu Zhou*, Shu-lei Zhau & Hong-kun Ma

 

 

 

The structural properties and vibrational mode of Fe(CN)n
(n=1-4) species have been examined by using HF, B3LYP, B3P86, and B3PW91 methods at 6-311G basis set level. The Fe(CN)n  species exhibit two states. For FeCN and Fe(CN)3 molecules, there are doublet (2∑) and quartet (4∑) states, while for Fe(CN)2 and Fe(CN)4 molecules, there are triplet (3∑) and quintet (5∑) states.

Notes

 

685

 

Synthesis and characterization of
non-oxovanadium(IV) complexes of biphenylphenols

 

 

 

 

 

 

 

 

 

 

 

 

 

Neeraj Sharma*, Meena, Maridula Thakur,
Vijay Kumar & S C Chaudhry

 

 

 

The non-oxovanadium(IV) complexes of composition
[VCl2-n (acac)2(OAr)n] and [VCl2-n(acac)2(OAr')n] [OAr = OC6H4C6H5-2; OAr'= OC6H4C6H5-4; acac = acetylacetonate ion (CH3COCHCOCH3); n = 1 and 2] have been synthesized by the reaction of [VCl2(acac)2] with the sodium salt of the respective phenols.

 

                    (where X = Ph-2 and Ph-4)

 

690

 

Pulse radiolytic studies on cis-dichlorobis-
(2,2
˘-bipyridine)cobalt(III) and cis-dichlorobis-
(1,10-phenanthroline)cobalt(III) complexes

 

 

 

Smita Ghosh, Vitthal A Kawade, Avinash V Sapre & Avinash S Kumbhar*

 

 

 

The reactions of hydrated electron (eˉaq) with Co(III) polypyridyl complexes of the type [Co(NN)2Cl2]Cl where NN =
2,2˘-bipyridine, and 1,10-phenanthroline have been studied by pulse radiolysis.

 

 

 

 

695

 

Theoretical study on magnetic coupling interactions of the binuclear copper(II) complexes

 

 

 

 

 

 

 

 

 

 

 

 

Ti-fang Miao & Shuang Li

 

 

 

The density functional theory has been used to calculate magnetic coupling constants of binuclear copper(II) complexes.  The results show that the coupled interaction between two magnetic centers is antiferromagnetic.

 

 

699

 

Borohydride reduction of azomethine bonds in
b-alanine Schiff base complexes

 

 

 

 

 

 

 

 

Bahattin Yalçın, Ajdar Akbar Medjidov,
Tarana Malik Nasrullayeva, Sülin Taşcıoğlu a  & 
Adnan Aydın*

 

 

 

Borohydride reduction of the azomethine bond in the Schiff base complexes of β-alanine has been studied. Ni(II), Pd(II) and Pt(II) complexes of N-β-carboxyethyl-2-hydroxynaphthyl­ideneimine , N-β-carboxyethyl-2-hydroxybenzylideneimine, and N-β-carboxyethyl-N-2-hydroxynaphtylmethyl­eneamine have been prepared. The reduction rates of Schiff bases and related activation energies have also been determined.

 

 

705

 

Oscillating behaviour of gallic acid – methyl ketone system catalysed by metal ions

 

 

 

 

 

 

 

Mushtaq A Lone, Masood A Nath,
Nadeem B Ganaie & Mustafa G Peerzada*

 

 

 

Studies on oscillatory behaviour of gallic acid with potassium bromate in presence of methyl ketones as co-substrates and various metal-ions as catalysts in aqueous acid medium are reported. The investigations establish the order of reactivity of single and mixed organic substrate systems and also explore the relative efficiency of metal ions as catalysts in the reaction systems. The Mn2+/Fe2+ couple has been examined for co-catalyst effect on both single and mixed organic substrate systems.

 

708

 

Statistical analysis on quencher in photobiological application

 

 

 

 

 

 

 

 

 

 

Jaydip Datta, Chiranjib Bhattacharjee* & B R De

 

 

 

The Stern-Volmer equation has been analysed statistically through linear regression or best fit method in presence of a quencher. The data obtained by the tryptophan fluorescence by dissolved oxygen gas as quencher at 348 nm has been analysed. The values of two most important photochemical kinetic parameters, the rate constant in presence of quencher and observed fluorescence lifetime in absence of quencher are found to be 1.276´1010 L.mol-1.s-1 and 2.6´10-10 s, respectively, with a correlation coefficient value of 1.000. This statistical data analysis is used to interpret the mechanism of bimolecular quenching which can be applied to photobiological study in the accessibility of amino acid residues of a folded protein to solvent.

 

 

Authors for correspondence are indicated by (*)


Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 643-649

 

Synthesis, structure, DNA-binding and photocleavage activity of a binuclear copper(II) complex

Ashis K Patra, Tarkeshwar Gupta, Sovan Roy & Akhil R Chakravarty*

Received 25 March 2008; accepted 9 April 2008

A binuclear copper(II) complex [Cu(L)(NO3)]2 (1), where L is a NSO-donor reduced Schiff base ligand derived from salicylaldehyde and 2-mercaptoethylamine, is prepared, structurally characterized as 1×0.5MeCN by single crystal X-ray diffraction method and its DNA binding and photo-induced DNA cleavage activity studied. Complex 1 has a diphenoxo-bridged binuclear structure with a {Cu2(m-OAr)2} core showing CuNO3S coordination at each metal centre. The redox active complex displays two quasi-reversible cyclic voltammetric responses at 0.26 V (DEp = 390 mV) and at -0.078 V (DEp = 375 mV) versus SCE in DMF-0.1 M TBAP at scan rate of 50 mV s-1. The complex exhibits a d-d band at 661 nm in DMF and shows moderate binding propensity to calf thymus DNA. It cleaves supercoiled (SC) DNA in the presence of 3-mercaptopropionic acid as a reducing agent. The complex is active in showing photo-induced cleavage of supercoiled pUC19 DNA in UV light of 365 nm and red light of 633 nm (He-Ne laser). The DNA photocleavage reaction involves formation of singlet oxygen (1O2) as the reactive species in a type-II pathway.

IPC Code: Int.Cl.8 C07F1/08

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 650-656

 

Synthesis, characterization and electrical conductivities of mixed-ligand (N, S/Se) heterobimetallic coordination polymers and their I2-doped products

Nanhai Singh* & Akhilesh Prasad

Received 15 February 2008; accepted 8 April 2008

New mixed-ligand heterometallic coordination polymers of the type [MM΄(Et2dtc)2(bzta)2], [MM˘(XCN)2(Et2dtc)2], [Cu2Hg(SCN)2(bzta)2] and [CuAg(SCN)(bzta)] [M = Ni(II) or Cu(II); M˘ = Ni(II), Zn(II), Cd(II), Hg(II), Pb(II) or 2Ag(I); X= S or Se; bzta- = benzothiazole-2-thiolate (C6H4NSCS-); Et2dtc- = diethyldithiocarbamate {(C2H5)2NCS2-}] have been prepared by reacting the above mixed-ligands and heterometal salts in a single-pot reaction and characterized by spectroscopic methods (IR, FT-Raman, Electronic and EPR), magnetic susceptibility, and conductivity measurements. All the complexes exhibit σrt close to 10-8 ohm-1 cm-1 and are insulators in the 303-393 K temperature range. The σrt of I2-doped products of some of the complexes are increased in 10-102 order of magnitude and show the behaviour of semiconductors over the given temperature range.

IPC Code: Int. Cl.8 C07F1/08; C07F1/10; C07F3/06; C07F3/08; C07F7/24; C07F15/04

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 657-662

 

Reactions of electron-deficient benzoquinoline triosmium cluster
[(
m-H)Os3(CO)9(m3-h2-C13H8N)] with diazomethane

Shariff E Kabira,*, Mohammad A Rahmana, Md. Nazim Uddina & Noorjahan Begumb

Received 7 January 2008; revised 26 March 2008

Treatment of the electron-deficient benzoquinoline triosmium cluster [(m-H)Os3(CO)9(m3-h2-C13H8N)] 1 with excess CH2N2 at 0 to 25°C leads to the formation of [(m-H)2Os3(CO)9{m3-h2-CH(C13H8N)}] 2 in 85% yield. Compound 2 is formed by insertion and subsequent C-H oxidative addition of a CH2 moiety into the ring C(8)-Os bond. Heating 2 at 98°C furnishes three new compounds [(m-H)3Os3(CO)8{m3-h2-C(C13H8N)}] 3, [(m-H)Os3(CO)9{m3-h2-C(C13H8N)}] 4, and [(m-H)2(Cl)Os3(CO)8{m3-h2-C(C13H8N)}] 5 in 18%, 23% and 8% yields, respectively. The formation of compounds 3 and 4 involves activation of the methylidene C-H bond. Compound 5 is most probably formed from 4 via exchange of a bridging hydride with a chloride. The trihydride compound 3 reacts with CCl4 at 77°C to give the dihydrido chloro-compound 5 in 44% yield. Thermolysis of 2 in the presence of H2 at 1 atm at 80°C gives 3 in 75% yield. All the new compounds have been characterized on the basis of elemental analyses, IR, NMR and mass spectroscopic data.

IPC Code: Int. Cl.8 C07F15/00

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 663-668

 

Synthesis of carbon nanotubes over transition metal ions supported on Al(OH)3

H Kathyayinia, K Vijayakumar Reddya, J B Nagyb & N Nagaraju*, a,b

Received 20 December 2007; revised 14 April 2008

Production of carbon nanotubes on bi-metallic (Fe/Co, Co/Ni, Fe/Ni, Fe/Mo, Co/Mo, Ni/Mo) and trimetallic (Fe/Co/Mo, Co/Ni/Mo, Fe/Ni/Mo) catalysts supported on Al(OH)3 by catalytic chemical vapor deposition is reported. The support-catalyst systems have been prepared by incipient dry impregnation method and characterized by BET, powder XRD, SEM, and TG/DSC techniques. The carbon nanotubes have been synthesized by allowing C2H2 and N2 to pass over a catalyst bed at 700°C placed on a quartz plate in a tubular furnace. The carbon deposit is examined using TEM. All the catalysts have been found to be active to different extents for the production of multiwall carbon nanotubes of varying thickness (10-15 nm). In the case of catalysts containing Fe/Co or Fe/Ni, a carbon deposit to an extent of 210 to 220% of the initial weight of the catalyst is obtained. This deposit also contains good quantities of carbon nanotubes. The tubes produced on nickel catalysts have been found to be thin and long. The effect of molybdenum on the nature of the carbon nanotubes produced is dependant on whether it is associated with one or two of the other transition metal ions supported over Al(OH)3. To synthesize good quantities of carbon nanotubes, a binary mixture of Fe, Co and Ni without Mo is the best.

IPC Code: Int. Cl.8 B01J21/00; B82B3/00

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 669-676

 

Correlation analysis of reactivity in the oxidation of substituted benzyl alcohols by morpholinium chlorochromate

Neelam Soni, Vandana Tiwari & Vinita Sharma*

Received 30 November 2007; revised 28 March 2008

Oxidation of benzyl alcohol and some ortho-, meta- and para-monosubstituted derivatives  by morpholinium chlorochromate in dimethyl sulphoxide leads to the formation of corresponding benzaldehydes. The reaction is first order each in both morpholinium chlorochromate and the alcohol. The reaction is promoted by hydrogen ions; the hydrogen-ion dependence has the form kobs= a + b [H+]. Oxidation of a,a-dideuteriobenzyl alcohol exhibits a substantial primary kinetic isotope effect (kH/kD = 5.86 at 298 K). The reaction has been studied in nineteen organic solvents and the effect of solvent analysed using Taft's and Swain's multi-parametric equations. The rates of oxidation of para- and meta-substituted benzyl alcohols have been correlated in terms of Charton’s triparametric LDR equation whereas the oxidation of ortho-substituted benzyl alcohols with tetraperametric LDRS equation. The oxidation of para-substituted benzyl alcohols is more susceptible to the delocalization effect than that of ortho- and meta- substituted compounds, which display a greater dependence on the field effect. The positive value of h suggests the presence of an electron-deficient reaction centre in the rate-determining step. The reaction is subjected to steric acceleration by the ortho-substituents. A suitable mechanism is also proposed.

IPC Code: Int. Cl.8  C07B33/00

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 677-684

 

Studies on the configuration and structural stability of cyanides Fe(CN)n (n=1-4)

Xue-jun Sun, Wen-juan Wang, Zheng-yu Zhou*, Shu-lei Zhau & Hong-kun Ma

Received 16 August 2007; revised 17 March 2008

The structural properties and vibrational mode of Fe(CN)n (n=1-4) species have been examined by using HF, B3LYP, B3P86, and B3PW91 methods at 6-311G basis set level. The Fe(CN)n (n=1-4) species exhibit two states. For FeCN and Fe(CN)3 molecules, there are doublet (2∑) and quartet (4∑) states, while for Fe(CN)2 and Fe(CN)4 molecules, there are triplet (3∑) and quintet (5∑) states. The ground state of FeCN is the doublet (2∑) state, both of which belong to Cv point group. For Fe(CN)2 species, the two states (3∑ and 5∑ states) have a V-type structure (C2v point group) and a linear structure (Dh point group), while the ground state is the quintet (5∑) state. In Fe(CN)3 species, the doublet (2∑) state (ground state) has a equilateral triangle structure belonging to D3h point group. But, the quartet (4∑) state has an isosceles triangle structure. The Fe(CN)4 species have a cubic (Td point group) structure in the triplet (3∑) state and a square(D4h point group) structure in the quintet (5∑) state.

IPC Code: Int. Cl.8 C01C3/12

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 685-689

 

Synthesis and characterization of non-oxovanadium(IV) complexes of biphenylphenols

Neeraj Sharma*, Meena, Maridula Thakur, Vijay Kumar & S C Chaudhry

Received 12 December 2007; revised 2 April 2008

The non-oxovanadium(IV) complexes of composition [VCl2-n(acac)2(OAr)n] and [VCl2-n(acac)2(OAr')n] [(OAr = OC6H4C6H5-2; OAr' = OC6H4C6H5-4; acac = acetylacetonate ion (CH3COCHCOCH3); n = 1 and 2)] have been synthesized by the reaction of [VCl2(acac)2] with the sodium salt of the respective phenols. The complexes have been characterized by elemental analyses, molar conductance measurements, molecular weight determinations and infra-red, electronic and FAB-MS spectral and magnetic moment studies. The room temperature magnetic moments of the complexes lying in the range 1.71-1.79 μB conform to vanadium (IV) oxidation state. Based upon these studies, monomeric distorted octahedral structures for the complexes have been proposed. The reactions of [VCl(acac)2(OAr)] and [VCl(acac)2(OAr')] with sodium alkoxides, NaOR (OR = OMe and OEt) afforded ternary complexes of type, [V(OR)(acac)2(OAr)] and [VOR(acac)2(OAr')], authenticated by physicochemical and infrared spectral studies.

IPC Code: Int. Cl.8 C07F9/00

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 690-694

 

Pulse radiolytic studies on cis-dichlorobis-(2,2˘-bipyridine)cobalt(III) and
cis-dichlorobis-(1,10-phenanthroline)cobalt(III) complexes

Smita Ghosh, Vitthal A Kawade, Avinash V Sapre & Avinash S Kumbhar*

Received 15 October 2007; revised 16 April 2008

The reactions of hydrated electron (eˉaq) with Co(III) polypyridyl complexes of the type [Co(NN)2Cl2]Cl where NN = 2,2˘-bipyridine (bpy), and 1,10-phenanthroline (phen) have been studied by pulse radiolysis. The rate constants for the reactions at 300 K have been evaluated to be (7.6±0.2)´1010, and (6.9±0.2)´1010 dm3 mol-1 s-1, respectively. Time resolved transient absorption spectra show two broad peaks at 360 and 610 nm for the bpy complex and a single broad peak at 420 nm for the phen complex at 1 ms. Comparison with reported transient spectra of the anion radicals of ligands indicates that the electron is located on the complex as a whole. The anion radicals of both the complexes initially produced, decay in the time scale of ~80 ms. Steady state absorption spectra on irradiation point out to breakdown of the phen complex, and the bpy-Co(III) complex is reduced to Co(II) complex. Conductance of the solution substantially increases on irradiation for both the complexes and can be attributed to aquation/de-ligation of the phen complex. The phen complex anion radical undergoes aquation/de-ligation by intramolecular electron transfer leading to dissociation of the complex. For bpy complex the conductance increases due to the release of chloride ions and reduction to Co(II) complex species is observed.

IPC Code: Int. Cl.8  C07F15/06

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 695-698

 

Theoretical study on magnetic coupling interactions of the binuclear copper(II) complexes

Ti-fang Miao & Shuang Li

Received 21 November 2007; revised 4 April 2008

The density functional theory (DFT) has been used to calculate magnetic coupling constants of binuclear copper(II) complexes. The results show that the coupled interaction between two magnetic centers is antiferromagnetic. The influence of electronegativity of atom far away from two magnetic centers on magnetic coupling interactions has been analyzed. The obtained results may be useful as reference for synthesis of the new functional complex and the molecular assembly analysis.

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 699-704

 

Borohydride reduction of azomethine bonds in b-alanine Schiff base complexes

Bahattin Yalçına, Ajdar Akbar Medjidovb, Tarana Malik Nasrullayevab, Sülin Taşcıoğlu a & Adnan Aydın a, *

Received 12 September 2007; revised 9 April 2008

Borohydride reduction of the azomethine bond in the Schiff base complexes of β-alanine has been studied. Ni(II), Pd(II) and Pt(II) complexes of N-β-carboxyethyl-2-hydroxynaphthyl­ideneimine (L1H2), N-β-carboxyethyl-2-hydroxybenzylideneimine (L2H2), and N-β-carboxyethyl-N-2-hydroxynaphtylmethyl­eneamine (L3H2) have been prepared. L1H2 forms complexes with palladium as Pd(L1H)2, in which carboxylic groups do not participate in the coordination. L2H2 and L3H2 behave as tridentate double charged ligands, giving complexes of the type ML2.nH2O and ML3.nH2O. Ni(II) gives binuclear complex [NiL3.2H2O]2. No visible reaction of –C=N- bond reduction with borohydride has been observed for the L1H2 complexes of Co(III) d6, Ni(II) d8, Pd(II) d8, Zn(II) d10 ions at 25oС in dimethyl formamide. This tendency has also been observed for Ni(II) complex of salicylaldehyde based β-alanine Schiff base, L2H2, as well as Ni(II), Pd(II), Zn(II) complexes of salen. However, the C=N bond can be reduced with borohydride when it coordinates the metal ions, Cu(II), Co(II) and Mn(II). Ni(II) complexes of both Schiff bases are inactive against reduction. The reduction rates of Schiff bases and related activation energies have also been determined.

IPC Code: Int. Cl.8 C07B31/00

 

Indian Journal of Chemistry

Vol 47A, May 2008, pp. 705-707

 

Oscillating behaviour of gallic acid – methyl ketone system catalysed by metal ions

Mushtaq A Lone, Masood A Nath, Nadeem B Ganaie & Mustafa G Peerzada*

Received 12 November 2007; revised 21 April 2008

Studies on oscillatory behaviour of gallic acid with potassium bromate in presence of methyl ketones as co-substrates and various metal-ions as catalysts in aqueous acid medium are reported here. The investigations establish the order of reactivity of single and mixed organic substrate systems and also explore the relative efficiency of metal ions as catalysts in the reaction systems. The Mn2+/Fe2+ couple has been examined for co-catalyst effect on both single and mixed organic substrate systems.

 

Indian Journal of Chemistry

Vol. 47A, May 2008, pp. 708-710

 

Statistical analysis on quencher in photobiological application

Jaydip Dattaa, Chiranjib Bhattacharjee*,b & B R Dea

Received 6 November 2007; revised 4 April 2008

The Stern-Volmer equation has been analysed statistically through linear regression or best fit method in presence of a quencher. Two important statistical parameters like regression coefficient and correlation coefficient are calculated from the standard data. The data obtained by the tryptophan fluorescence by dissolved oxygen gas as quencher at 348 nm has been analysed. The values of two most important photochemical kinetic parameters, the rate constant in presence of quencher and observed fluorescence lifetime in absence of quencher are calculated. The values obtained by this type of analysis are: 1.276´1010 L.mol-1.s-1 and 2.6´10-10 s respectively, with a correlation coefficient value of 1.000. This statistical data analysis is used to interpret the mechanism of bimolecular quenching which can be applied to photobiological study in the accessibility of amino acid residues of a folded protein to solvent.