Synthesis and Characterization of Transition-Metal Complexes of 2-prop-2-en-1-yl-N-hydroxyprop-2-ene-1-sulfinimidothioate Oxime
DOI:
https://doi.org/10.63682/jns.v13i1.9957Keywords:
Metal chelates, Sulfinimidothioate oxime ligand, Coordination chemistry, Transition-metal complexesAbstract
In order to examine their coordination behaviour and physicochemical characteristics, a number of transition-metal chelates of 2-prop-2-en-1-yl-N-hydroxyprop-2-ene-1-sulfinimidothioate oxime were created and described. The ligand was synthesized and subsequently interacted with metal salts under regulated pH, temperature, and reflux conditions. With yields ranging from moderate to good (51–58%), representative complexes, such as CdL1 and CuL1, were produced as colourful crystalline solids. Successful complexation was confirmed by clear optical changes, as the copper complex (CuL1) formed an orange solid (58% yield) while the cadmium chelate (CdL1) appeared as a reddish-brown solid (51% yield). The syntheses were optimized by keeping slightly acidic to neutral pH (5.5–6.5) using dilute ammonia and by employing methanol as the reaction medium under continuous stirring and controlled heating. FT-IR, UV-Vis spectroscopy, CHNS elemental analysis, ICP-MS metal estimation, mass spectrometry, NMR spectroscopy, TGA, and X-ray diffraction were used to thoroughly characterize each metal chelate. The analytical results verified the hypothesized molecular formulae and stoichiometries (e.g., C₁₂H₂₀CuN₂O₂S₄³⁻ for CuL1 and C₁₂H₂₀CdN₂O₂S₄²⁻ for CdL1) and indicated coordination through oxime and sulfinimidothioate functional groups. Thermal and spectroscopic studies further demonstrated complex stability and ligand–metal interactions. This study presents a systematic approach for synthesizing and analysing sulphur–nitrogen donor chelating ligands and their metal complexes, contributing to the knowledge of their structural and possible functional uses.
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References
[1] Wong, J.S.Y. and Wong, W.T., 2002. Synthesis, structural characterization and reactivity of triosmium carbonyl clusters containing oxime ligands. New Journal of Chemistry, 26(1), pp.94-104. https://doi.org/10.1039/B107628K
[2] Akl, M.A., Al-Awadhi, M.M. and El-Zeny, A.S., 2023. Divalent transition metal complexes of nitrogen, oxygen and sulfur containing ligand: design, structural, spectral, pH-metric, theoretical molecular modeling, analytical and mechanism studies. Applied Water Science, 13(10), p.195. https://doi.org/10.1007/s13201-023-01988-1
[3] Kukushkin, V.Y. and Pombeiro, A.J., 1999. Oxime and oximate metal complexes: unconventional synthesis and reactivity. Coordination Chemistry Reviews, 181(1), pp.147-175. https://doi.org/10.1016/S0010-8545(98)00215-X
[4] Akl, M.A., El-Asmy, A.A. and Yossef, W.M., 2005. Separation via flotation, spectrophotometric speciation, and determination of vanadium (IV) in wastes of power stations. Analytical sciences, 21(11), pp.1325-1335. https://doi.org/10.2116/analsci.21.1325
[5] Akl, M.A., Hashem, M.A., Ismail, M.A. and Abdelgalil, D.A., 2022. Novel diaminoguanidine functionalized cellulose: synthesis, characterization, adsorption characteristics and application for ICP-AES determination of copper (II), mercury (II), lead (II) and cadmium (II) from aqueous solutions. BMC chemistry, 16(1), p.65. https://doi.org/10.1186/s13065-022-00857-3
[6] Júnior, O.K., Gurgel, L.V.A., de Freitas, R.P. and Gil, L.F., 2009. Adsorption of Cu (II), Cd (II), and Pb (II) from aqueous single metal solutions by mercerized cellulose and mercerized sugarcane bagasse chemically modified with EDTA dianhydride (EDTAD). Carbohydrate Polymers, 77(3), pp.643-650. https://doi.org/10.1016/j.carbpol.2009.02.016
[7] Garcia-Sanchez, R., Bettmer, J. and Ebdon, L., 2004. Development of a new method for the separation of vanadium species and chloride interference removal using modified silica capillaries-DIN-ICP-MS. Microchemical journal, 76(1-2), pp.161-171. https://doi.org/10.1016/S0026-265X(03)00158-9
[8] Kenawy, I.M., Hafez, M.A.H., Ismail, M.A. and Hashem, M.A., 2018. Adsorption of Cu (II), Cd (II), Hg (II), Pb (II) and Zn (II) from aqueous single metal solutions by guanyl-modified cellulose. International journal of biological macromolecules, 107, pp.1538-1549. https://doi.org/10.1016/j.ijbiomac.2017.10.017
[9] Naushad, M., Ahamad, T., Alothman, Z.A. and Al-Muhtaseb, A.A.H., 2019. Green and eco-friendly nanocomposite for the removal of toxic Hg (II) metal ion from aqueous environment: adsorption kinetics & isotherm modelling. Journal of Molecular Liquids, 279, pp.1-8. https://doi.org/10.1016/j.molliq.2019.01.090
[10] Hokkanen, S., Repo, E., Suopajärvi, T., Liimatainen, H., Niinimaa, J. and Sillanpää, M., 2014. Adsorption of Ni (II), Cu (II) and Cd (II) from aqueous solutions by amino modified nanostructured microfibrillated cellulose. Cellulose, 21(3), pp.1471-1487. https://doi.org/10.1007/s10570-014-0240-4
[11] Khir, N.A.F.M., Razak, M.R.M.A., Nordin, F.J., Sofyan, N.R.F.M., Rajab, N.F. and Sarip, R., 2021. Synthesis, antiproliferative and antimalarial activities of dinuclear silver (I) complexes with triphenylphosphine and thiosemicarbazones ligands. Indonesian Journal of Chemistry, 21(3), pp.575-587. https://doi.org/10.22146/ijc.57343
[12] Wattanakanjana, Y., Janwatthana, K., Romyen, T. and Nimthong-Roldán, A., 2021. Crystal structures of copper (I) and silver (I) chloride complexes containing 4-phenylthiosemicarbazide and triphenylphosphine ligands. Asian J. Exp. Sci, 47(28), pp.10-2306. http://dx.doi.org/10.2306/scienceasia1513-1874.2021.S001
[13] Sharma, P., Nath, H., Frontera, A., Barcelo-Oliver, M., Verma, A.K., Hussain, S. and Bhattacharyya, M.K., 2021. Biologically relevant unusual cooperative assemblies and fascinating infinite crown-like supramolecular nitrate–water hosts involving guest complex cations in bipyridine and phenanthroline-based Cu (ii) coordination compounds: Antiproliferative evaluation and theoretical studies. New Journal of Chemistry, 45(18), pp.8269-8282. https://doi.org/10.1039/D1NJ01004B
[14] Dehno Khalaji, A.A., Shahsavani, E., Dusek, M., Kucerakova, M. and Eigner, V., 2020. Synthesis, Characterization, and Crystal Structures of a Thiosemicarbazone Ligand and Its Silver (I) Complex. Iranian Journal of Chemistry and Chemical Engineering, 39(4), pp.23-28. https://doi.org/10.30492/ijcce.2019.35000
[15] Anu, D., Naveen, P., Devendhiran, T., Shyamsivappan, S., Kumarasamy, K., Lin, M.C., Frampton, C.S. and Kaveri, M.V., 2021. Synthesis, spectral characterization, X-ray crystallography and biological evaluations of Pd (II) complexes containing 4 (N)-substituted thiosemicarbazone. Journal of Coordination Chemistry, 74(21-24), pp.3153-3169. https://doi.org/10.1080/00958972.2021.2025222
[16] Kotian, A., Kamat, V., Naik, K., Kokare, D.G., Kumara, K., Neratur, K.L., Kumbar, V., Bhat, K. and Revankar, V.K., 2021. 8-Hydroxyquinoline derived p-halo N4-phenyl substituted thiosemicarbazones: Crystal structures, spectral characterization and in vitro cytotoxic studies of their Co (III), Ni (II) and Cu (II) complexes. Bioorganic Chemistry, 112, p.104962. https://doi.org/10.1016/j.bioorg.2021.104962
[17] Damit, N.S.H.H., Hamid, M.H.S.A., Rahman, N.S.R.H.A., Ilias, S.N.H.H. and Keasberry, N.A., 2021. Synthesis, structural characterisation and antibacterial activities of lead (II) and some transition metal complexes derived from quinoline-2-carboxaldehyde 4-methyl-3-thiosemicarbazone. Inorganica Chimica Acta, 527, p.120557. https://doi.org/10.1016/j.ica.2021.120557
[18] Singh, N.K., Shrestha, S., Shahi, N., Choudhary, R.K., Kumbhar, A.A., Pokharel, Y. and Yadav, P., 2021. Anticancer potential of N (4) substituted 5-nitroisatin thiosemicarbazones and their copper (II) complexes. Rasayan J. Chem, 14(1600.10), p.31788. http://doi.org/10.31788/
[19] Pelagatti, P., Venturini, A., Leporati, A., Carcelli, M., Costa, M., Bacchi, A., Pelizzi, G. and Pelizzi, C., 1998. Chemoselective homogeneous hydrogenation of phenylacetylene using thiosemicarbazone and thiobenzoylhydrazone palladium (II) complexes as catalysts. Journal of the Chemical Society, Dalton Transactions, (16), pp.2715-2722. https://doi.org/10.1039/A804052D
[20] Aly, S.A. and Fathalla, S.K., 2020. Preparation, characterization of some transition metal complexes of hydrazone derivatives and their antibacterial and antioxidant activities. Arabian Journal of Chemistry, 13(2), pp.3735-3750. https://doi.org/10.1016/j.arabjc.2019.12.003
[21] Zülfikaroğlu, A., Ataol, Ç.Y., Çelikoğlu, E., Çelikoğlu, U. and İdil, Ö., 2020. New Cu (II), Co (III) and Ni (II) metal complexes based on ONO donor tridentate hydrazone: Synthesis, structural characterization, and investigation of some biological properties. Journal of Molecular Structure, 1199, p.127012. https://doi.org/10.1016/j.molstruc.2019.127012.
[22] Abouzayed, F.I., Emam, S.M. and Abouel-Enein, S.A., 2020. Synthesis, characterization and biological activity of nano-sized Co (II), Ni (II), Cu (II), Pd (II) and Ru (III) complexes of tetradentate hydrazone ligand. Journal of Molecular Structure, 1216, p.128314. https://doi.org/10.1016/j.molstruc.2020.128314
[23] Hassan, A.M., Elbialy, Z.I. and Wahdan, K.M., 2020. Synthesis, Characterization, Biological and Antitumor Activity of Co (II), Ni (II), Cu (II) and Zn (II) Complexes of N-(2-Chlorophenyl)-N′-Benzoyl Thiourea. Organic & Medicinal Chemistry International Journal, 9(3), pp.125-137. http://dx.doi.org/10.19080/OMCIJ.2020.09.555767
[24] Adjissi, L., Chafai, N., Benbouguerra, K., Kirouani, I., Hellal, A., Layaida, H., Elkolli, M., Bensouici, C. and Chafaa, S., 2022. Synthesis, characterization, DFT, antioxidant, antibacterial, pharmacokinetics and inhibition of SARS-CoV-2 main protease of some heterocyclic hydrazones. Journal of Molecular Structure, 1270, p.134005. https://doi.org/10.1016/j.molstruc.2022.134005
[25] Abkari, A., Chaabane, I. and Guidara, K., 2016. DFT (B3LYP/LanL2DZ and B3LYP/6311G+ (d, p)) comparative vibrational spectroscopic analysis of organic–inorganic compound bis (4-acetylanilinium) tetrachlorocuprate (II). Physica E: Low-dimensional Systems and Nanostructures, 81, pp.136-144. https://doi.org/10.1016/j.physe.2016.03.010
[26] Kumar, S., Devi, J. and Ghule, V.D., 2022. Synthesis, spectral analysis, DFT-assisted studies, in vitro antioxidant and antimicrobial activity of transition metal complexes of hydrazone ligands derived from 4-nitrocinnemaldehyde. Research on Chemical Intermediates, 48(8), pp.3497-3525. https://doi.org/10.1007/s11164-022-04769-8
[27] El-Tabl, A.S., Mohamed Abd El-Waheed, M., Wahba, M.A. and Abd El-Halim Abou El-Fadl, N., 2015. Synthesis, Characterization, and Anticancer Activity of New Metal Complexes Derived from 2‐Hydroxy‐3‐(hydroxyimino)‐4‐oxopentan‐2‐ylidene) benzohydrazide. Bioinorganic chemistry and applications, 2015(1), p.126023. https://doi.org/10.1155/2015/126023
[28] Tolan, D.A., Kashar, T.I., Yoshizawa, K. and El‐Nahas, A.M., 2021. Synthesis, spectral characterization, density functional theory studies, and biological screening of some transition metal complexes of a novel hydrazide–hydrazone ligand of isonicotinic acid. Applied Organometallic Chemistry, 35(6), p.e6205. https://doi.org/10.1002/aoc.6205.
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