Kinetic parameters and thermal decomposition for Novel 1,1-Malonyl-bis(4-p-Chlorophenylthiosemicarbazide) and Cu(II), Co(II), Zn(II) and Sn(II) complexes(H₄pClMaTS) synthesized by electrochemical method

Ragab R. Amin, Yamany B. Yamany, Mohamed Abo-Aly, Ali M. Hassan

.

DOI: 10.4236/ns.2011.39103                

Abstract

Anodic oxidation of Co, Cu, Zn, and Sn metals in an acetone solution of 1,1-malonayl-bis(4-p- Chlorophenylthiosemicarbazide) yields complexes of composition with general formula [Co₂(pClMaTS)(H₂O)₆]·2H₂O, [Cu₂(pClMaTS)(H₂O)₆], [Zn₂(pClMaTS)(H₂O)₆] and [Sn₂(pClMaTS)(H₂O)₆]·2H₂O. Chelation was investigated based on elemental analysis, conductivity, magnetic moment, spectral (UV-Vis, IR, Raman, 1HNMR, mass), thermal, and ESR studies. The Raman and infrared spectral studies suggests the tridentate behavior of the ligand from each tail. Since the ligand has two thiose- micarbazide groups, it may acts in an SNO tridentate fashion from each side with one of the two metal ions forming a polynuclear complex coordinating through both of the lone pair of electrons the enolic oxygen of the carbonyl group (C=O), the azomethine nitrogen (C=N) and the thioenol form of the thiocarbonyl group (C=S). The differential thermogravimetric analysis (DTG) curves were used to study the decomposition steps of the isolated complexes using Horowitz-Metzger (HM) and Coats-Redfern (CR) methods. The kinetic thermodynamic parameters such as: E*, ΔH*, ΔS*and ΔG* are calculated from the DTG curves.

Keywords

Metal(II) Complexes; Electrochemical; Thermogravimetric; Bis-Thiosemicarbazide

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Zhao, Y. (2000) Liquid chromatographic determination of chelates of cobalt(II), copper(II) and iron(II) with 2- thiophe-necarboxald-hyde-4-phenyl-3-thiosemicarbazone. Chromatographia, 51, 231-234. doi:10.1007/BF02490570
[2]	Khuhawar, M.Y. and Lanjwani, S.N. (1998) Liquid chromatographic determination of cobalt(II), copper(II) and iron(II) using 2-thiophenaldehyde-4-phenyl-3-thiosemi- carbazone as derivatizing reagent. Talanta, 46, 485-490. doi:10.1016/S0039-9140(97)00213-0
[3]	Lunn, G., Phillips, L.R. and Pacula-Cox, C. (1998) Reversed phase high performance liquid chromatography of 4-(2-pyridyl)-1-piperazinethio-carboxylic acid 2-[1-(pyridyl) ethylidene] hydrazide dihydrochloride, a synthetic thiosemicarbazone with anti-tumour activity. Journal of Chromatography B: Biomedical Sciences and Applications, 708, 217-222. doi:10.1016/S0378-4347(97)00637-3
[4]	Hoshi, S., Higashihara, K., Suzuki, M., Sakurada, Y., Sugawara, K., Uto, M. and Akatsuka, K. (1997) Simultaneous determination of platinum(II) and palladium(II) by reversed phase high-performance liquid chromatography with spectrophotometric detection after collection on and elu-tion from resin coated with dimethylglyoxal bis-(4- phenyl-3-thiosemicarbazone). Talanta, 44, 571-576. doi:10.1016/S0039-9140(96)02064-4
[5]	Gismera, M.J., Mendiola, M.A., Procopio, J.R. and Sevilla, M.T. (1999) Copper potentiometric sensors based on copper complexes containing thiohydrazone and thiosemicar-bazone ligands. Analytica Chimica Acta, 385, 143-149. doi:10.1016/S0003-2670(98)00840-X
[6]	Qu, J.Y., Liu, M. and Liu, K.Z. (1999) Simultaneous determination of lead and copper by carbon paste electrodes modified with pyruvaldehyde bis (NN’-dibutyl thiosemicarbazone). Analytical Letters, 32, 1991-2006.
[7]	West, D.X., Carlson, C.S., Liberta, A.E. and Scovil, J.P. (1990) The chemical and antifungal properties of the Copper (II) complexes of 2-acetyl-pyrazine 4N-methyl-, 4N-di-methyl-, and 3-hexamethyleneiminyl-thio-semicarba- zone. Transition Metal Chemistry, 15, 383-387. doi:10.1007/BF01177467
[8]	West, D.X., Carlson, C.S., Liberta, A.E., Albert, J.N. and Daniel, C.R. (1990) Transtion metal ion complexes of thiosemicarba-zones derived from 2-Acetylpyridine. Transition Metal Chemistry, 15, 341-344. doi:10.1007/BF01177458
[9]	Chohan, Z.H. (2009) Metal-based antibacterial and antifun-gal sulfonamides: synthesis, characterization, and biological properties. Transition Metal Chemistry, 34, 153- 161. doi:10.1007/s11243-008-9171-y
[10]	Liu, M.C., Lin, T.S., Penketh, P. and Sartorelli, A.C. (1995) Synthesis and antitumor activity of 4- and 5-substituted de-rivatives of isoquinoline-1-carboxalde- hyde thiosmicar-bazone. Journal of Medicinal Chemistry, 38, 4234-4243. doi:10.1021/jm00021a012
[11]	Liu, M.C., Lin, T.S., Cory, J.G., Cory, A.H. and Sartorelli, A.C. (1996) Synthesis and biological Activity of 3- and 5-amino derivatives of pyridine-2-carboxaldehyde thiosemicar-bazone. Journal of Medicinal Chemistry, 39, 2586-2593. doi:10.1021/jm9600454
[12]	Zhu, X., Wang, C., Lu, Z. and Dang, Y. (1997) Synthesis, Charac-terization and biological activity of the Schiffbase de-rived from 3,4-dihydroxybenz-aldehyde and thiosemi- carbazide and its metal complexes with Nickel(II) and Iron(II). Transition Metal Chemistry, 22, 9-13. doi:10.1023/A:1018453316348
[13]	Lim, J.K., Mathias, C.J. and Green, A.M. (1997) Mixed- bis(thiosemi-carbazone) ligands for the preparation of copper radiopharmaceuticals: Synthesis and evaluation of tetradentate ligands containing two dissimilar thiosemi- carbazone functions. Journal of Medicinal Chemistry, 40, 132-136. doi:10.1021/jm9605703
[14]	Sathisha, M.P., Budagumpi, S., Kulkarni, N.V., Kurdekar, G.S., Revankar, V.K. and Pai, K.S.R. (2010) Synthesis, structure, electro-chemistry and spectral characterization of (d-glucopyra-nose)-4-phenylthiosemicarbazide metal complexes and their antitumor activity against Ehrlich Ascites Carcinoma in Swiss albino mice. European Jour- nal of Medicinal Chemistry, 45, 106-113. doi:10.1016/j.ejmech.2009.09.031
[15]	Mostafa, M.M. (2007) Spectroscopic studies of some thio-semicarbazide compounds derived from Girard’s T and P. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 66, 480-486. doi:10.1016/j.saa.2006.02.063
[16]	El-Shekeil, A., Al-Yusufy, F., Amin, R.R. and Abdullah, A. (2004) The DC Electrical Conductivity of the Direct Electro-chemically Synthesized Poly (azome-thine-thio- semicarb-zone)-metal complexes. Journal of Inorganic and Organometallic Polymers, 14, 131-148. doi:10.1023/B:JOIP.0000028091.50660.3a
[17]	Sladjana, B., Novakovi?, G.A. and Bogdanovi?, L.V.M. (2005) Transition metal complexes with thiosemicarba- zide-based ligands and the supramolecular arrangement in the Ni(II) complexes of S-methy-lisothiosemicarbazide. Inorganic Chemistry Communications, 8, 9-13. doi:10.1016/j.inoche.2004.10.001
[18]	Vukadin, M.L., Sla?ana, B.N., Bogdanovi?, G.A., Jokso- vi?, M.D. and Mészáros, K. (2007) Transition metal complexes with thio-semicarbazide-based ligands. Part LVI: Nickel(II) complex with 1,3-diphenylpyrazole-4- carboxaldehyde thiosemicarbazone and unusually defor- med coordination geometry. Polyhedron, 26, 3783-3792. doi:10.1016/j.poly.2007.04.012
[19]	El-Asmy, A.A., Al-Ansi, T.Y., Amin, R.R., El-Shahat, M.F., Structural studies on cadmium(II), Co(II), Cu(II) Ni(II) and Zn(II) complexes of 1-malonyl bis(4-phenyl- thiosemi-carbazide. Transition Metal Chemistry, 15, 12- 15.
[20]	El-Asmy, A.A., Al-Ansi, T.Y., Amin, R.R. and Mounir, M. (1990) Spectral, magnetic and electrical properties of 1-succinyl bis (4-phenylthiosemicarbazide) complexes. Polyhedron, 9, 2029-2034. doi:10.1016/S0277-5387(00)84032-2
[21]	Amin, R.R. (2010) Chemical and Electrochemical prepara-tion for Co(II) complexes of some pyri-dine-2- (1H)-thione-3-cyano-4-(2-methylphenyl)-5,6-ring fused cycloalkane derivatives. Journal of Phos-Phorus, Sulfur, and Silicon and the Related Elements, 185, 537-543. doi:10.1080/10426500902840861
[22]	Amin, R.R. and El-Gemeie, G.E.H. (2001) The direct electro-chemical synthesis of Co(II), Ni(II) and Cu(II) com-plexes of some pyridinethione derivatives. Synthesis Reactivity Inorganic and Nanometal-Organic Chemistry, 31, 431-440. doi:10.1081/SIM-100002230
[23]	Refat, M.S., El-Deen, I.M., Amin, R.R. and El-Ghol, S. (2010) Spectroscopic studies and biological evaluation of some transition metal complexes of a novel schiff base li-gands derived from 5-arylazo-salicyladehyde and o-amino phenol. Toxicological & Environmental Chemistry, 92, 1093-1110. doi:10.1080/02772240903252173
[24]	Refat, M.S., El-Deen, I.M., Anwer, Z.M. and El-Ghol, S. (2009) Bivalent transition metal complexes of coumarin-3-ylthio-semicarbazone derivatives: Spectroscopic, antibacterial activity and thermogravimetric studies. Journal of Molecular Structure, 920, 149-162. doi:10.1016/j.molstruc.2008.10.059
[25]	Rajesh, K. and Dennis, G.T. (1989) The direct electro- chemical synthesis of metal complexes of 2,2’-dipyridy- lamine. Inorganica Chimica Acta, 157, 51-56.
[26]	Furniss, B.S., Hannaford, A.J. Smith, P.W.G. and Tatchell, A.R. (1991) Vogel’s textbook of practical organic chemi- stry. Longman Scientific and Technical, John Wiely & Sons, Inc., New York.
[27]	El-Metwally, N.M., El-Shazly, R.M., Gabr, I.M. and El-Asmy, A.A. (2005) Physical and spectroscopic studies on novel vanadyl complexes of some substituted thio- semi-carbazides. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61, 1113-1119. doi:10.1016/j.saa.2004.06.027
[28]	El-Asmy, A.A., Al-Gammal, O.A., Dena, A.S. and Ghazy, S.E. (2009) Synthesis, characterization, molecular modeling and eukaryotic DNA degradation of 1-(3,4-dihydro- xybenzylidene) thiosemicarbazide com-plexes. Journal of Molecular Structure, 934, 9-22. doi:10.1016/j.molstruc.2009.05.039
[29]	Refat, M.S. and Killa, H.M.A. (2010) Hammad fetooh, spectro-scopic and thermal characterization of Cu(II), Co(II), Ni(II) and Mn(II) complexes of fluorescent dye 4-N,N-dimethyl-ethanolamine-N-allyl-1,8-naphthalimide (4DMEAN). Journal of Molecular Structure, 983, 122- 132. doi:10.1016/j.molstruc.2010.08.041
[30]	Chandra, S. and Kumar, U. (2005) Spectral and magnetic studies on manganese(II), cobalt(II) and nickel(II) complexes with Schiff bases. Spectrochimica Acta A, 61, 219-24. doi:10.1016/j.saa.2004.03.036
[31]	Hassaneien, M.M., Gabr, I.M., Abdel-Rhman, M.H. and El-Asmy, A.A. (2008) Synthesis and structural investigation of mono- and polynuclear copper complexes of 4-ethyl-1-(pyridin-2-yl) thiosemicarbazide. Spectrochimica Acta Part A, 71, 73-79. doi:10.1016/j.saa.2007.11.009
[32]	Lever, A.B.P. (1988) Inorganic electronic spectroscopy. Elsevier Publishing Company, Amsterdam, 318-361.