J.

Atoms and Molecules / 2(6); 2012 / 410420 Research Article

Narendra Wanjari et al

Journal of Atoms and Molecules

An International Online Journal
ISSN 2277 1247

MICROWAVE ASSISTED SYNTHESIS, CHARACTERIZATION AND THERMAL DEGRADATION STUDIES OF COORDINATION POLYMERS OF 1-(2,4-DIHYDROXY-5(1-(HYDROXYAMINO)ETHYL)-3-NITROPHENYL) ETHANONE OXIME Narendra Wanjari*1, L.J. Paliwal1, M.B. Bagade2
1

Department of Chemistry, Rashtrasant Tukadoji Maharaj, Nagpur University, Nagpur-033 2 PG, Department of Chemistry, Seth Kesarimal Porwal College, Kamptee 441002 (INDIA) Revised on: 18-12-2012 Accepted on: 26122012

Received on: 09-12-2012 Abstract:

Microwave heating has received considerable attention as a powerful synthetic tool for metal complexes in many fields of Inorganic chemistry and material Science. Since, the 1990s numerous metal complexes have been synthesized using the microwave technique. However, only few of studies have been discussed on such synthesis. In this communication, we focus on microwave assisted synthesis of ligand (DHNO) and its coordination polymers. The dioxime ligand H2L, is synthesized by the reaction of 3-nitro 4, 6-diacetylresorcinol with hydroxylamine hydrochloride in molar ratio 1:2. The ligand is characterized by using IR, 1H NMR and mass spectroscopy. A detail thermal study of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) coordination polymers with1-(2,4-dihydroxy5-(1-(hydroxyamino)ethyl)-3-nitrophenyl)ethanone oxime is being reported. Freeman-Carroll and Sharp-wentworth methods have been used to calculate activation energy and thermal stability of these polymers. Kinetic parameters have been calculated using the data of freeman-carroll-method. Elemental analysis, UV-visible, Thermal analysis, magnetic susceptibility, as well as electrical conductivity and infrared spectral measurements are used to elucidate the structures of the coordination polymers. Thermo gravimetric analysis (TGA) is used as tool to detect the water molecules associated with the coordination polymers are either coordinated or crystalline. Key Words: Microwave, Coordination polymers, Thermal studies and kinetic parameters. Introduction:
[1-5] The structural importance and [6] of metal complexes derived applications from bis- bidentate and bis-multidentate chelates promoted us to undertake the study of coordination properties of such ligand. The present work is devoted to the study of the coordination chemistry of 1-(2, 4-dihydroxy5-(1-(hydroxyamino) ethyl)-3-phenyl) ethanone oxime with M (II) transition metal

* Corresponding author Narendra Wanjari, Email: narendra_nru2007@rediffmail.com

Tel: +91 9850534622

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J. Atoms and Molecules / 2(6); 2012 / 410420 ions. A large amount of work has been reported[7-15]on the synthesis, characterization, and thermal studies of several coordination polymers. The present paper gives a detail study of thermal degradation of polymeric chelates of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) formed with 1-(2,4-dihydroxy-5-(1(hydroxyamino)ethyl)-3-phenyl)ethanone oxime abbreviated as (DHNO). Method for estimating kinetic parameters from dynamic TG studies are mostly based on assumption that the Arrhenius equation is valid and that the thermal and diffusion barriers are negligible. It has been pointed out that properly designed coordination polymers of transition metals should have semi conductive properties, and the formation of semi conductive coordination polymers has indeed been observed. An attempt was also made to prepare semiconductors having suitable band gap for a potential use in the electronics industries [16, 17]. Material and Methods: All chemicals used were of analytical reagent grade. Solvents were distilled before used. Preparation of the Ligand (DHNO) Synthesis of 1-(2,4-dihydroxy-5-(1(hydroxyamino)ethyl)-3-nitrophenyl)ethanone oxime was carried out by conventional method. A solution of hydroxylamine hydrochloride (0.7g 0.01 m) in alcohol with 3-nitro, 4,6-diacetylresorcinol (1.195g 0.005m), refluxing it on water bath for 4-5 hours.[18] The reaction was monitored by TLC. Light green coloured product obtained. Product was recrystallized with hot aqueous alcohol. (Decomposition point > 225 0C) m/z =270 Yield 50%. Microwave Technique The initial reactant 4,6-diacetylresorcinol was synthesised by treating resorcinol, acetic anhydride and zinc chloride in equimolar ratio All rights reserved 2011

Narendra Wanjari et al under microwave irradiation (33%) for two minutes with constant interval of time followed by treating 50% HCl in water. Recrystallized with methanol. Melting point = 178 0c m/z=195 yield=50 %. A solution of hydroxylamine hydrochloride (0.7g 0.01m) in alcohol with 3-nitro 4,6 diacetylresorcinol (1.195g 0.005m) irradiated with 33% radiation on the microwave for 20 minute with constant interval of time. Preparation of Polychelates The coordination polymers have been prepared by irradiating the solution of ligand and metal acetate in the stoichiometric ratio (1:1) in the minimum volume of solvent ( 50% DMF-alcohol) under 33% radiation for 5-10 minutes [ 19-20] with constant interval. The polymer was then washed with water, DMF, and acetone. Product was dried in vacuum desiccator. These coordination polymers were found to be insoluble in almost all organic solvents such as alcohol, acetone, chloroform, DMF and DMSO. Properties All chelate polymers are coloured solid which are insoluble in common organic solvents. It was not possible to characterize the polymers by conventional method, like osmometry, viscometry, conductometry etc. as they are insoluble. All of them are thermally stable up to 250 0C. Measurements Microanalysis for C, H, and N were carried out on Eassuperuser, Elemental Analyser system GmbH: VarioEL Superuser, RACHI. IR spectra in the region of 400-4000 cm-1 were recorded in the solid state (KBr pallets) in the Department of Pharmacy, Rashtrasant Tukadoji Maharaj Nagpur University, NAGPUR, on FTIR-101A SHIMADZU. Reflectance spectra were scanned on UV1800 SHIMAZDU spectrophotometer in the www.jamonline.in 411

J. Atoms and Molecules / 2(6); 2012 / 410420 range of 200-800nm. The thermal study of all the coordination polymers have been carried out on fabricated TGA apparatus at Department of Chemistry, Rashtrasant Tukadoji Maharaj, Nagpur University Nagpur in the range of 20 - 700 0C and heating rate was 10 0C min-1 in air atmospheric condition. Analytical Procedures The metal content of each polymer was determined by gravimetric method. In this method, about 0.1 to 0.2 g of the coordination polymer was accurately weighed in a crucible and decomposed simply by heating it in air carefully, first gently (~ 250 0C) for about 10 minutes and then strongly(~ 800 0C) for about 3 hours until constant weight was obtained. The residue was weight as oxide (Mn2O3, Co2O2, NiO, CuO and ZnO). Physical Methods All Physico-chemical measurements were carried out at room temperature. Magnetic measurements were made on a Sartorius semi-micro Gouy balance at room temperature using Hg [Co (NCS) 4] as calibrant. The thermogravimetric results were recorded at heating rate of 10 0C min -1. For the electrical conductivity measurements at various temperatures powdered dry polychelates were made in to pallets in a hydraulic press under the pressure of 10 tons. The sample pallets were coated with colloidal graphite on both sides for good electrical contact and mounted between the two brass electrodes of the sample holder. The resistance was measured with model CCS-01 scientific equipment and services Roorkee, India. Results and discussion The ligand DHNO is used in the present investigation for the synthesis of various polychelates with various metal ions. The 44.51 (44.60)

Narendra Wanjari et al elemental analysis (Table2) suggest 1:1 (metal: ligand) stoichiometric for the chelate polymers. They also suggest the possibility of the coordination of water molecules in all the chelate polymers. The association of water molecules in chelate polymers have also been observed by earlier workers.[21] This seem to be reasonable since water allows the metal ions to reach the maximum coordination number of six. Thermal Behaviour and studies Thermogram of DHNO and its polychelates are shown in figure 2.The perusal of the thermogram of the polychelates indicates that all are nearly identical. The rate of thermal decomposition of the ligand is higher than that of polychelates at all temperature. Comparatively, all the polychelates were found to be thermally more stable than DHNO. Thermal analyses also confirm the presence of water molecules in all polychelates. In general, the water of hydration may be considered as either crystal or coordination water.
NOH OH NO2 NOH OH

Fig. 1. Structure of DHNO Ligand

Table 1. Elemental analysis of ligand DHNO)

Ligand Carbon % Hydrogen% Nitrogen%

DHNO Found

Found

Found

(Calculated) (Calculated) (Calculated) 4.19 (4.08) 15.83 (15.61)

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Table 2. Elemental analysis of DHNO coordination polymers C% Found (calculated) 30.67 (30.45) 30.32 (30.15) 31.01 (31.57) 32.23 (32.69) 32.54 (32.60) H% Found (calculated) 4.54 (4.31) 4.65 (4.27) 3.78 (3.94) 3.78 (3.54) 3.68 (3.53) N% Found (calculated) 10.79 (10.65) 10.43 (10.55) 11.34 (11.04) 11.67 (11.44) 11.78 (11.41) M% Found (calculated) 13.72 (13.94) 14.89 (14.82) 15.75 (15.52) 17.39 (17.63) 17.89 (17.66)

S.N.

Coordination polymers

1 2 3 4 5

{[Mn(II)(DHNO)(H2O)2]2H2O}n {[Co(II)(DHNO)(H2O)2]2H2O}n {[Ni(II)(DHNO)(H2O)2]H2O }n {[Cu(II)(DHNO)(H2O)2]}n {[Zn(II)(DHNO)(H2O)2]}n

Table 3. Physico-chemical properties of DHNO coordination polymers. S. No. Coordination polymers Colour Empirical Formula 1 2 3 4 5 {[Mn(II)(DHNO)(H2O)2]2H2O}n {[Co(II)(DHNO)(H2O)2]2H2O}n {[Ni(II)(DHNO)(H2O)2]H2O }n {[Cu(II)(DHNO)(H2O)2]}n {[Zn(II)(DHNO)(H2O)2]}n Black Dark yellow Green Dark Green Light yellow MnC10O10 N3H17 CoC10O10N3H17 NiC10O9N3H15 CuC10O8N3H13 ZnC10O8N3H13 Formula weight 394 398 380 367 368

According to Nikolaev et al., [22] water eliminated below 150 0C can be considered as crystal water, and water eliminated above 150 0 C may be due to its coordination to metal atom present in the chelates. In the present study there is weight loss up to 150 0C, indicating the presence of crystal water in all of the polychelates except Cu (II) and Zn (II) polychelates. However, the removal of water above 150 0C in the case of Mn (II), Co (II), Ni (II) chelates indicates the presence of All rights reserved 2011

coordinated water molecules. The order of thermal stability in terms of the half decomposition temperature has been found to be Ni > Cu = Zn > Co > Mn.

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J. Atoms and Molecules / 2(6); 2012 / 410420

100

Narendra Wanjari et al

5
90 80 70

% Residue

60 50 40

1
30 20 10 0 0 100 200 300 400 500 600 700

3 2 4

Temperature

Fig. 2. Thermogram of 1) DHNO, 2) Mn(II) DHNO, 3) Co(II) DHNO, 4) Ni(II) DHNO, 5) Cu(II) DHNO, 6) Zn(II) DHNO.

To determine the kinetic parameters of the coordination polymers Freeman-Carroll [23] and Sharp-Wentworth [24] methods have been used. Freeman-Carroll Method The dynamic thermal analysis of all coordination polymers has been carried out from room temperature to 700 0C in the air atmosphere. In this method, following expression is used to evaluate various kinetic parameters:

Hence by plotting
log(dW/dt) (1 / T ) versus logW logW r

n is obtained as an intercept on former axis and Ea is the slope of the line. Sharp-Wentworth Method The following expression is used to evaluate activation energy:
log( dC/dt ) = log( A / ) ( E a / 2.303R ) 1 / T 1- C

log(dW/dt) (1 / T ) = ( Ea / 2.303 R ) +n logW logW r

Where dW/dt is the rate of change of weight with time, Wr = Wc-W, where Wc is the weight loss at completion of reaction or at definite time t, T is the temperature, R is the gas constant, and n is the order of reaction.

Where is the linear heating rate, dT / dt Therefore, a linear plot of

dC/dt ) versus 1 / T 1- C is obtained, whose slope gives the value of Ea and A may be evaluated from intercept. The linear relationship confirmed that assumed order (n=1) is correct. log(

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Table 4. Results of thermogravimetric analysis of DHNO and its polychelates (Heating rate = 10 0C min-1).
Coordination polymers Activation Energy (Ea)/kJ mol-1 Entropy change (S) / JK1 mol-1 Free energy change (F)/kJ Frequen cy factor (Z)/S-1 (S*)/J (n) Apparent entropy change Order of reaction Half Decomp osition temperature

FC (DHNO) {[Mn(II)(DHNO)(H2O)2.2H2O]}n {[Co(II)(DHNO)(H2O)2 .2H2O]}n {[Ni(II)(DHNO)(H2O)2]H2O}n {[Cu(II)(DHNO)(H2O)2]}n {[Zn(II)(DHNO)(H2O)2]}n 23.58 20.77 19.09 21.57 22.36 21.75

SW 23.55 20.67 19.02 21.59 22.22 21.86 -154.59 -155.26 -156.13 -155.27 -154.86 -154.95 92.84 75.58 77.33 76.38 77.03 79.55 1024.00 1946.70 1293.89 1127.19 1609.53 1306.17 -48.42 -47.70 -48.19 -48.41 -48.04 -48.25 1.09 1.04 1.11 1.09 1.07 1.05 523 0K 483 0K 523 0K 568 0K 563 0K 563 0K

Electronic spectra and Magnetic Moment. Mn (II) Polychelate. The UV-visible reflectance spectrum of Mn (II) polychelate shows intense band at 16.72 kK which may be ascribed to the octahedral stereochemistry of the chelate polymer. This band may be assigned to 6A1g4T1g transition. The

observed magnetic moment 5.43 B.M. however is lower than the spin-only value (5.92 B.M.) for five unpaired electrons. The lowering may be due to partial air oxidation of Mn (II) to Mn(III) during synthesis [25] or due to spin exchange in the solid state of the complex.

Table 5. Magnetic moment and electronic spectral data of DHNO polychelates.

S.No. 1 2 3 Coordination polymers {[Mn(II)(DHNO)(H2O)2]2H2O}n {[Co(II)(DHNO)(H2O)2]2H2O}n {[Ni(II)(DHNO)(H2O)2]H2O}n eff (B.M.) 5.43 4.88 3.10 Absorbance/kK 16.72 kK 14.08kK 14.72kK Assignments
6

Stereochemistry Octahedral Octahedral Distorted octahedral octahedral

A1g4T1g T1g(F)4T2g(F) A2g2 3T1g(F) B1g2A1g B1g2Eg -

{[Cu(II)(DHNO)(H2O)2]}n

1.90

12.47kK 16.31kK -

2 2

{[Zn(II)(DHNO)(H2O)2]}n

Octahedral

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J. Atoms and Molecules / 2(6); 2012 / 410420 Co (II) Polychelate. The diffused reflectance spectrum of Co (II) polychelate depicts region of absorption, around 14.08 kK. The most probable assignment for the Co (II) octahedral chelate can be given as 4T1g(F)4T2g(F). The magnetic moment (4.88 B.M.) is in the range required for high spin octahedral stereochemistry. Ni (II) Polychelate. The UV-visible reflectance spectrum of Mn (II) polychelate exhibits intense band at 14.72 kK which may be ascribed to the distorted octahedral stereochemistry of the chelate polymer. This band may be assigned to 3A2g2 3T1g (F) transition. The observed magnetic moment 3.10 B.M. Cu (II) Polychelate. The UV-visible reflectance spectrum of Cu (II) polychelate displays two bands at 12.47, and 16.31kK. A broad band at 16.31 kK suggests a octahedral

Narendra Wanjari et al geometry. Two visible bands are expected in the spectra of octahedral complexes corresponding to the transitions 2B1g2Eg for 613 nm and 2B1g2A1g for 801 nm. The observed magnetic moment 1.90 B.M. this is also indicative of the octahedral geometry. Zn (II) Polychelate. The Zn (II) polychelate is diamagnetic and has octahedral geometry. NMR spectrum of DHNO The ligand DHNO exhibits signals at 2.35, 8.1, 12.8, and 13.4 (ppm) as shown in figure 3. A sharp signal at 2.35 (ppm) may be assigned to CH3 protons. The presence of sharp signal at 13.4 (ppm) may be attributed to the presence of proton of =NOH. A strong sharp signal at 8.1 (ppm) is attributed to the proton of aromatic ring [26-28]. A peak at 11.8 (ppm) is correspond to aromatic OH protons.

Fig 3. NMR spectrum of ligand.

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J. Atoms and Molecules / 2(6); 2012 / 410420 Infrared Spectra The IR spectrum of DHNO displays broad and strong sharp band at 3417 cm-1 assignable to oxime (OH), stretching vibration of ligand. The broadening of the (OH) stretching bands are most likely due to inter and intramolecular hydrogen bonding. The reaction of DHNO with metal ions yields amorphous polymers which are stable in atmosphere. The IR spectra of polychelates do not contain (OH) band of free ligand indicating that the proton on the oxime (OH) is lost upon chelation with metal ions. This is attributed to deprotonation of group during chelation. Further the shift in the (CO) band to high frequency confirms

Narendra Wanjari et al coordination through the phenolic oxygen in the ligand. The (N-O) band of the oxime is observed at 1035 cm-1 [29] which appears in chelate polymers in the region 910 to 980 cm1 indicating bonding of N-O-H....O intra molecular bonding. Similarly, observed band at 1631 cm-1 in DHNO is attributed to stretching mode of C=N group. This frequency is shifted to 1579-1595 cm-1 upon chelation with metal ions indicating the involvement of C=N group in chelation. The bands observed in all coordination polymers around 449-485 cm-1 may be assigned to the M-N mode. The band observed around 611705 cm-1 in coordination polymers may be assigned to the M-O mode.

Table 6: IR spectral assignments of DHNO and its coordination polymers cm-1.

Sr. No. 1 2 3 4 5 6 Comp. (OH) (C=O) (C=N) (C-O) (N-O) H 2O 3450 3304 3150 3228 3250 H 2O 1520 1579 1593 H 2O 865 842 890 (M-O) (M-N)

(DHNO) {[Mn(II)(DHNO)(H2O)2.2H2O]}n {[Co(II)(DHNO)(H2O)2 .2H2O]}n {[Ni(II)(DHNO)(H2O)2]H2O}n {[Cu(II)(DHNO)(H2O)2]}n {[Zn(II)(DHNO) (H2O)2]}n

3417 -

1631 1595 1579 1597 1583 1590

1242 1145 1105 1105 1109 1110

1035 995 960 965 977 975

705 675 665 611 680

455 485 465 474 460

H NO2 H2O O M C N H2O H3C O

O CH3 N C O NO2 H H y H2O

O CH3 C N O H2O H2O

H NO2 O M N C CH3 O n

Fig 4. The proposed structure of coordination polymers of DHNO Ligand, M=metal ions, Mn (II), Co (II), Ni (II), Cu (II), Zn (II). yH2O- lattice water. y= 1 for Ni (II), coordination polymers. y=2 for Mn (II), Co (II) coordination polymers. Y=0 for Cu (II), Zn (II) coordination polymer. All rights reserved 2011 www.jamonline.in 417

J. Atoms and Molecules / 2(6); 2012 / 410420 Electrical Conductivity Semiconducting behaviour was systematically explored by Spiratos et al. [30]. Patel et al. have studied the electrical conductivity of chelate polymers and an industrially useful semiconducting material has been reported [31] . The conductivity measurements were made over a wide range of temperatures. The electrical conductivity varies exponentially with the absolute temperature according to following relationship: = 0 exp (-Ea/RT)
.

Narendra Wanjari et al (ii) The electrical conductivity of coordination polymers of DHNO increases in the order of Zn < Ni < Co < Mn < Cu at room temperature. This order is in good agreement with the order reported earlier.
[32]

(iii)The activation energy of electrical conduction of coordination polymers has been found to increase in the order of Co < Zn < Cu < Ni < Mn which is in partial agreement with the order reported by earlier workers. [33] (iv) The plot of log verses 1/T was found to be linear in the temperature range under study (Fig. 5) which indicates that a linear relationship has been followed. (v) The results indicate that the electrical conductivity and the activation energy of electrical conduction of the chelate polymers varies with the metal ion in the polychelates. This may be due to the incorporation of different metal ions in the polymer.[32]

Where Ea is the activation energy of the semiconductor and 0 is a constant which provides a measure of carrier mobility. The results of electrical conductivity measurements of polychelates are incorporated in table 7. Figure 5 depicts the effect of temperature on the electrical conductivity of the chelates. From the results of electrical conductivity (Table 7) the following conclusions may be drawn: (i) In the coordination polymers of DHNO their electrical conductivity at room temperature lies in the range of 1.55 x 10-8 to 2.27 x 10-8 (ohm cm)-1

Table 7. Electrical data for polychelates. (T K)a (ohm cm) -1 Temperature (K) (308) (373) (308) (373) (308) (373) (308) (373) (308) (373) Ea d (eV) 0.026 0.011 0.017 0.015 0.014

Compound

1.96 x 10-8 {[Mn(II)(DHNO)(H2O)2.2H2O]}n 2.13 x 10-8 1.82 x 10-8 {[Co(II)(DHNO)(H2O)2 .2H2O]}n 1.96 x 10-8 1.73 x 10-8 {[Ni(II)(DHNO)(H2O)2]H2O }n 1.94 x 10-8 {[Cu(II)(DHNO)(H2O)2]}n 2.04 x 10-8 2.27 x 10-8 {[Zn(II)(DHNO)(H2O)2]}n 1.55 x 10-8 1.77 x 10-8

308373 308373 308373 308373 308373

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Narendra Wanjari et al

(T K)a = Electrical conductivity at temperature shown in parentheses. Tb = Temperature range in which electrical conductivity was measured. Ead = Activation energy for electrical conduction in (eV) of polychelates.

1000/T (K-1)
2.6 2.7 2.8 2.9 3 3.1 3.2 3.3 3.4

-7.5

-7.6

log

-7.7

-7.8

4 1 2 3 5

-7.9

Fig 5. Temperature dependence of log of polychelates: 1) Mn (II) DHNO 2) Co (II) DHNO 3) Ni (II) DHNO 4) Cu (II) DHNO 5) Zn (II) DHNO.

Conclusions [1] The chelate polymers have found to be distinct colours and insoluble in common organic solvents. The presence of lattice water was determined on the basis of infrared, thermal studies and CHN analyses. [2] On the basis of elemental analysis, infrared and reflectance spectra, and thermal studies the {[Mn(II)(DHNO)(H2O)2.2H2O]}n and {[Co(II)(DHNO)(H2O)2 .2H2O]}n coordination polymers have octahedral geometry, {[Ni(II)(DHNO)(H2O)2]H2O}n coordination polymer has distorted octahedral geometry, {[Cu(II)(DHNO)(H2O)2]}n and {[Zn(II)(DHNO)(H2O) 2]}n coordination polymers have octahedral geometries.

Acknowledgements Authors are thankful to the Head of Department of Chemistry; Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, for providing the laboratory facilities. References 1) 2) Frankline K.J., M.F Richardson, Inorg. Chem. 1980, 19 (7), 2107-2113. Thompson D. M., W Balenovich, L. H. M. Hornich, M.F. Richardson, Inorg.Chim. Acta 1980, 46(5), 199-203. Thomas T.W., A.E. Underhill, Chem. Soc. Rev.1972,1(1), 99-120. Endress H., H.J. Keller, R. Lehmann, A. Poveda, H.H, Rupp, H. Van de Sand, Z. Naturforsch. 1977,32B, 516-527.

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