Tolyl/benzyl dithiocarbonates of zinc(II) [( CH3C6H4 and C6H5CH2OCS2)2Zn] have been synthesized in 1?:?2 molar ratio by the reaction of zinc chloride, ZnCl2, with sodium salts of tolyl/benzyl dithiocarbonates CS2Na, in aqueous medium. These complexes were further reacted with nitrogen and phosphorous donor ligands to obtain donor stabilized complex of the type [[( CH3C6H4 and C6H5CH2)OCS2]2Zn.nL], (L = Bipy, Phen for and PPh3, Py for ). These complexes were characterised by elemental analysis, mass, IR, and NMR (1H, 13C, and 31P) spectroscopies. The thermal analysis (TGA/DTA), cyclic voltammetry, and SEM have also been done. Distorted tetrahedral and octahedral geometries around the Zn(II) metal are proposed. These complexes have depicted potential antibacterial and antifungal activity. 1. Introduction Dithiocarbonates are sulfur and oxygen containing ligands which display rich and varied coordination chemistry with a wide range of transition and main group metals [1]. Transition metal dithiolate complexes exhibited versatile and interesting chemistry that have been studied extensively during the last decades [2]. Xanthates can form bidentate, monodentate, or network solids, showing a wide range of coordination behaviour [3–6]. More recent applications of xanthates and other thiocompounds are in the production of nanoparticles of metal sulphides [7, 8] and NLO properties [9, 10]. Metal xanthates are extensively used as corrosion inhibitors [11] and agricultural reagents [12, 13]. Dithiocarbonates have also found important use in medicine as antitumor agents [14, 15] and for treating Alzheimer’s disease [16]. Sodium and potassium ethylxanthate have antidotal effects in acute mercurial poisoning [17] and recently as coadjuvant in AIDS treatment [18]. The –OCS2 group of xanthates makes them more reactive towards various metals [19]. Zinc is an essential element and plays an important role in biochemical processes [20]. Ability of zinc(II) to coordinate with strategic ligand can lead to a structural and functional model for zinc metalloenzymes [21]. Zinc complexes of 1, 1-dithiolato ligands and their adducts with neutral ligands are known but not all dithiolate ligands have received the same attention [22]. Surprisingly, in spite of years of chemistry of the extensive and long-term use of alkyl xanthates as ligands [23–28], structural and spectroscopic characterizations have been rather limited with regard to the aryl xanthates [29]. Fackler et al. [29], however, reported the synthesis of thallium aryl xanthates which in turn were used for the metathetical
References
[1]
S. Ghoshal and V. K. Jain, “Gallium(III) and indium(III) dithiolate complexes: versatile precursors for metal sulfides,” Journal of Chemical Sciences, vol. 119, no. 6, pp. 583–591, 2007.
[2]
A. O. G?rgülü, H. ?elikkan, and M. Arslan, “The synthesis, characterization and electrochemical behavior of transition metal complexes containing nitrogen heterocyclic sulphur donor ligand,” Acta Chimica Slovenica, vol. 56, no. 2, pp. 334–339, 2009.
[3]
G. Winter, “Inorganic xanthates,” Reviews in Inorganic Chemistry, vol. 2, pp. 253–342, 1980.
[4]
E. R. T. Tiekink and G. Winter, “Inorganic xanthates: a structural perspective,” Reviews in Inorganic Chemistry, vol. 12, pp. 183–302, 1992.
[5]
B. F. Hoskins and C. D. Pannan, “A novel five-co-ordinate pentagonal-planar complex: X-ray structure of the tris-(O-ethyl xanthato)tellurate(II) anion,” Journal of the Chemical Society, Chemical Communications, no. 11, pp. 408–409, 1975.
[6]
D. Dakternieks, R. Di Giacomo, R. W. Gable, and B. F. Hoskins, “Synthesis, NMR study, and crystal structures of bis(diethyldithiocarbamato)-(O,O′-diethyl dithiophosphato)phenyltellurium(IV), PhTe(S2CNEt2)2[S2P(OEt)2], and bis(diethyldithiocarbamato)iodomethyltellurium(IV), MeTe(I)(S2CNEt2)2,” Journal of the American Chemical Society, vol. 110, no. 20, pp. 6762–6768, 1988.
[7]
K. Xu and W. Ding, “Controlled synthesis of spherical CuS hierarchical structures,” Materials Letters, vol. 62, no. 29, pp. 4437–4439, 2008.
[8]
Q. Han, J. Chen, X. Yang, D. Lu, and X. Wang, “Preparation of uniform Bi2S3 nanorods using xanthate complexes of bismuth (III),” Journal of Physical Chemistry C, vol. 111, no. 38, pp. 14072–14077, 2007.
[9]
D. E. Zelmon, Z. Gebeyehu, D. Tomlin, and M. Th. Copper, “Investigation of transition metal-xanthate complexes for nonlinear optical applications,” Material Research Society Symposia Proceeding, vol. 519, pp. 395–401, 1998.
[10]
N. Kalgotra, B. Gupta, K. Kumar, and S. K. Pandey, “O-tolyldithiocarbonate complexes of iron(II) and iron(III),” Phosphorus, Sulfur and Silicon and the Related Elements, vol. 187, no. 3, pp. 364–375, 2012.
[11]
M. Scendo, “Potassium ethyl xanthate as corrosion inhibitor for copper in acidic chloride solutions,” Corrosion Science, vol. 47, no. 7, pp. 1738–1749, 2005.
[12]
W. M. Doane, B. S. Shasha, and C. R. Russel, “Encapsulation of pesticides within starch matrix,” Controlled Release Pesticides, vol. 53, pp. 74–83, 1977.
[13]
W. J. Orts, R. E. Sojka, and G. M. Glenn, “Polymer additives in irrigation water to reduce erosion and better manage water infiltration,” Agro Food Industry Hi-Tech, vol. 13, no. 4, pp. 37–41, 2002.
[14]
A.-C. Larsson and S. ?berg, “Study on potassium iso-propylxanthate and its decomposition products: experimental 13C CP/MAS NMR Combined with DFT calculations,” Journal of Physical Chemistry A, vol. 115, no. 8, pp. 1396–1407, 2011.
[15]
R. M. Adibhatla, J. F. Hatcher, and A. Gusain, “Tricyclodecan-9-yl-Xanthogenate (D609) mechanism of actions: a mini-review of literature,” Neurochemical Research, vol. 37, pp. 671–679, 2012.
[16]
M. Perluigi, G. Joshi, R. Sultana et al., “In vivo protection by the xanthate tricyclodecan-9-yl-xanthogenate against amyloid β-peptide (1-42)-induced oxidative stress,” Neuroscience, vol. 138, no. 4, pp. 1161–1170, 2006.
[17]
S. Shahzadi, S. Ali, R. Jabeen, and M. K. Khosa, “[Pd(Me-Xanthate)2]: synthesis, characterization, and X-ray structure,” Turkish Journal of Chemistry, vol. 33, no. 2, pp. 307–312, 2009.
[18]
O. A. G?rgülü, M. Arslan, and E. ?il, “Synthesis and characterization of potassium 1,3-bis(N-methylpiperazino) propan-2-O-xanthate and the complexes of Co(II), Ni(II) and Cu(I) ions,” Journal of Coordination Chemistry, vol. 59, no. 6, pp. 637–642, 2006.
[19]
A. K. Malik, K. N. Kaul, B. S. Lark, W. Faubel, and A. L. J. Rao, “Spectrophotometric determination of cobalt, nickel palladium, copper, ruthenium and molybdenum using sodium isoamylxanthate in presence of surfactants,” Turkish Journal of Chemistry, vol. 25, no. 1, pp. 99–105, 2001.
[20]
F. A. Cotton and G. Willkinson, Advance Inorganic Chemistry, Wiley-Interscience, New York, NY, USA, 5th edition, 1988.
[21]
L. E. da Silva, P. T. de Sousa Jr., A. C. Joussef, C. Piovezan, and A. Neves, “Synthesis, structure and physicochemical properties of zinc and copper complexes based on sulfonamides containing 8-aminoquinoline ligands,” Quimica Nova, vol. 31, no. 5, pp. 1161–1164, 2008.
[22]
I. Ara, F. E. Bahij, M. Lachkar, and N. B. Larbi, “Synthesis and characterization of ethylxanthato complexes of zinc(II) with P-donor ligands,” Transition Metal Chemistry, vol. 28, no. 8, pp. 908–912, 2003.
[23]
M. J. Cox and E. R. T. Tiekink, “Crystal structure of tris(O-isopropyldithiocarbonato)cobalt(III), C12H21CoO3S6,” Zeitschrift fur Kristallographie, vol. 211, no. 10, pp. 753–754, 1996.
[24]
R. F. Klevtsova, L. A. Glinskaya, T. G. Leonova, and S. V. Larionov, “Mixed-ligand complexes Zn(2,2′-Bipy)(ROCS2)2 with mono- and bidentate ligands ROCS-2 (R = i-Pr, i-Bu),” Journal of Structural Chemistry, vol. 43, no. 1, pp. 125–132, 2002.
[25]
A. A. Mohamed, I. Kani, A. O. Ramirez, and J. P. Fackler Jr., “Synthesis, characterization, and luminescent properties of dinuclear gold(I) xanthate complexes: X-ray structure of [Au2(nBu-xanthate)2],” Inorganic Chemistry, vol. 43, no. 13, pp. 3833–3839, 2004.
[26]
K. Hussain Reddy and P. Sambasiva Reddy, “Mixed ligand zinc(II) and cadmium(II) complexes with alkyl xanthates and 2,2′-bipyridyl,” Indian Journal of Chemistry A, vol. 40, no. 10, pp. 1118–1120, 2001.
[27]
A. V. Ivanov, O. A. Bredyuk, O. N. Antzutkin, and W. Forsling, “Copper(II) and Nickel(II) alkylxanthate complexes (R = C2H5, i-C3H7, i-C4H9, s-C4H9, and C5H11): EPR and solid-state 13C CP/MAS NMR studies,” Russian Journal of Coordination Chemistry, vol. 30, no. 7, pp. 480–485, 2004.
[28]
W.-S. Sie, J.-Y. Jian, and K.-B. Shiu, “Synthesis, characterization and photophysical properties of iridium(III) Bis-cyclometallated complexes containing 1,1-dithiolates,” Journal of the Chinese Chemical Society, vol. 58, no. 5, pp. 611–616, 2011.
[29]
J. P. Fackler Jr., D. P. Schussler, and H. W. Chen, “Sulfur chelates 29. Ni(II), Pd(II), Pt(II), Co(III) and Cu(I, II) complexes of O-phenyldithiocarbonates,” Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, vol. 8, no. 1, pp. 27–42, 1978.
[30]
B. Gupta, N. Kalgotra, S. Andotra, and S. K. Pandey, “O-Tolyl/benzyl dithiocarbonates of phosphorus(III) and (V): syntheses and characterization,” Monatshefte fur Chemie, vol. 143, pp. 1087–1095, 2012.
[31]
A. I. Vogel, A Textbook of Quantitative Inorganic Analysis, Longmans, London, UK, 3rd edition, 1961.
[32]
K. Nakamoto, Infrared and Raman Spectra of Inorganic Compounds, Wiley-Interscience, New York, NY, USA, 4th edition, 1986.
[33]
B. G. Tweedy and C. Loeppky, “The use of 14C-labeled glucose, glucuronate, and acetate to study the effect of atrazine, simazine, and fluometuron on glucose catabolism in selected plant pathogenic fungi,” Phytopathology, vol. 58, no. 11, pp. 1522–1531, 1968.
[34]
D. P. Singh, V. Malik, R. Kumar, and K. Kumar, “Template synthesis of macrocyclic complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II): spectroscopic, antibacterial and antifungal studies,” Journal of the Serbian Chemical Society, vol. 75, no. 6, pp. 763–772, 2010.
[35]
I. Ara, F. El Bahij, and M. Lachkar, “Synthesis, characterization and X-ray crystal structures of new ethylxanthato complexes of zinc(II) with N-donor ligands,” Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, vol. 36, no. 5, pp. 399–406, 2006.
[36]
A. Decken, R. A. Gossage, M. Y. Chan, C. S. Lai, and E. R. T. Tiekink, “Bis(N,N-dibenzyldithiocarbamato)zinc(II),” Applied Organometallic Chemistry, vol. 18, no. 2, pp. 101–102, 2004.
[37]
N. A. Abdul Ghafar, I. Baba, B. M. Yamin, and S. W. Ng, “(2,2′-Bipyridine-κ2 N,N′)bis-(N-ethyl-N-methyldithiocarbamato-κ2 S,S′)zinc(II),” Acta Crystallographica E, vol. 66, part 2, no. 2, p. m208, 2010.
[38]
R. F. Klevtsova, L. A. Glinskaya, T. G. Leonova, and S. V. Larionov, “Two modifications of the mixed-ligand complex ZnPhen(i-C3H7OCS2)2 with monodentate and bidentate ligands i-C3H7OCS2-,” Journal of Structural Chemistry, vol. 42, no. 2, pp. 244–250, 2001.