Synthesis and Structural Characterization of Homo Dinuclear Phosphorus 1,1-Dithiolate Cd(II) Complexes

Year 2023, , 759 - 774, 30.04.2023

Ertuğrul Gazi Sağlam , Elif Bulat , Mustafa Saçmacı , Servet Yıldız

https://doi.org/10.29130/dubited.1104231

Abstract

In this study, 2,4-bis(3-methoxytolyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide which is formulated as [((CH3)C6H3(OCH3)-P(S)S)2] compound was resynthesized. From this, two dithiophosphonic acids which were previously known were synthesized from the reaction of this compound with alcohols ([HS2P(R’)(ORn)], HLn; R’=(CH3)C6H3(OCH3); R1= Ethyl-, L1; R2= 2-propyl-, L2). These acids were converted to corresponding ammonium salts, ([NH4][Ln]). The ammonium salts were further reacted with CdCl2.H2O to prepare dinuclear three new dithiophosphonato cadmium(II) complexes, ([Cd(μ-Ln)2(Ln)2]) in ethanol medium. Structures of the complexes were characterized by elemental analysis, mass spectrometry (ESI), FT-IR, Raman, NMR (1H, 13C, 31P)
spectroscopy.

Keywords

Phosphorus 1, 1-Dithiolates, Dithiadiphosphetanes, Dithiophosphonic Acid, Cd(II)Dithiophosphonato Complexes

Çift Metal Merkezli Fosfor 1,1-Ditiyolat Cd(II) Komplekslerinin Sentez ve Yapılarının Aydınlatılması

Abstract

Bu çalışmada, 2,4-bis-(3-metoksitolil)-1,3-ditiya-2,4-difosfetan 2,4-disülfür ([((CH3)C6H3(OCH3)-P(S)S)2]) bileşiği yeniden sentezlendi. Bu bileşiğin alkollerle reaksiyonundan literatürde bilinen iki ditiyofosfonik asiti ([HS2P(R’)(ORn)], HLn; R’=(CH3)C6H3(OCH3); R1= Etil-, L1, R2= 2-propil-, L2) sentezlendi. Ham ditiyofosfonik asitler kuru amonyak gazıyla ligandlarına ([NH4][S2P(R’)(ORn)]) dönüştürüldü. Etil alkol ortamında bu ligandların kadmiyum tuzlarıyla reaksiyonlarından çift çekirdekli yeni ditiyofosfonato Cd(II) kompleksleri sentezlendi ([Cd(μ-Ln)2(Ln)2]). Komplekslerin yapıları; elementel analizi, kütle spektrometresi (ESI), FT-IR, Raman, NMR (1H, 13C, 31P) spektroskopisiyle aydınlatıldı.

Keywords

Fosfor 1,1-Ditiyolatlar, Ditiyadifosfetanlar, Ditiyofosfonik Asit, Cd(II) Ditiyofosfonato Kompleksleri

References

• [1] W.E., Van Zyl, “Dithiophosphonates and Related P/S-Type Ligands of Group 11 Metals”, Com. Inorg. Chem., vol.31, no.1-2, pp. 13-45, 2010.
• [2] S. Kelebek, P.F. Wells, S.O. Fekete, “Selective flotation process for separation of sulphide minerals,” US5411148A, 2005.
• [3] A. Chaves., E.R. Pohl, L. Vecere, L. Hwang, “Organofunctional silanes and their mixtures,” US 7,919,650, 2011.
• [4] S. F.Valle, A. S. Giroto, H. P. G. Reis, G. G. F. Guimarães, C. Ribeiro, “Synergy of Phosphate- Controlled Release and Sulfur Oxidation in Novel Polysulfide Composites for Sustainable Fertilization,” J. Agric. Food Chem., vol.69, no.8, pp. 2392–2402, 2021.
• [5] B.R. Dohner, “Additive compositions for lubricants and functional fluids,” US 5,902,776, 1999.
• [6] M.A. Nicholls, P .R Norton, M. Kasrai, G.M. Bancroft, “Review of the lubrication of metallic surfaces by zinc dialkyl-dithiophosphates,” Tribology Int., vol.38, pp. 15-39, 2005.
• [7] T. Colclough, S.J. Brois, “Heavy metal salts of dithiophosphonate compounds,” US 4,900,852, 1990. [8] Shaub, H., “Mixed antioxidant composition,” US 6,306,802, 2001.
• [9] T.J. Ajayi, M.N. Pillay, W.E. van Zyl, “Solventfree mechanochemical synthesis of dithiophosphonic acids and corresponding nickel(II) complexes,” Phosphorus, Sulfur, and Silicon, vol. 192, no. 11, pp. 1205-1211, 2017.
• [10] W.E. Van Zyl, J.P. Facler, “A General And Convenient Route To Dithiophosphonate Salt Derivatives,” Phosphourus, Sulfur And Silicon, vol. 167, pp. 117-132, 2000.
• [11] I. Haiduc, “1,1-Dithiolato Ligands in Comprehensive,” Coordination Chemistry II, 2004, vol. 1, pp. 349-376.
• [12] K. Diemert, W. Kuchen, “Zur Kenntnis der Organophosphorverbindungen XVII1, Dithiophosphinsauren RR’P(S)SH, Ihre Synthese, Derivate und MetallKomlexe,” Phosphorus, Sulfur Silicon, vol. 3, no. 2, pp. 131–136, 1977.
• [13] S. Kumar, R. Khajuria, V.K. Gupta, R. Kant, S.K. Pandey, “The first nickel(II) complexes of disubstituted diphenyldithiophosphates: Synthesis, spectroscopic, electrochemical, antifungal and single crystal X-ray analysis,” Polyhedron, vol. 72, pp. 140–146, 2014.
• [14] M. Karakuş, I. Kara, Ö. Çelik, I. Orujalipoor, S. İde, H. Yılmaz, “Synthesis, characterization, single crystal structure and theoretical studies of trans-Ni(II)-complex with dithiophosphonate ligand,” J. Mol. Struct., vol. 1163, pp. 128–136, 2018.
• [15] M. Karakuş, P. Lönnecke, E. Hey-Hawkins, “Zwitterionic ferrocenyldithiophosphonates: the molecular structure of [FcP(S)S(OCH2CH2NH2Me)] [Fc = Fe(η5-C5H4)( η5-C5H5)],” Polyhedron, vol. 23, pp. 2281–2284, 2004.
• [16] W.E. Van Zyl, J.D.Woollins, “The Coordination Chemistry of Dithiophosphonates: An Emerging And Versatile Ligand Class,” Coord. Chem. Rev., vol. 257, no. 3-4, pp. 718– 773, 2013.
• [17] I. Haiduc, D.B. Sowerby, S.F. Lu, “Stereochemical aspects of phosphor-1,1-dithiolato metal complexes (dithiophosphates, dithiophosphinates): Coordination patterns, molecular structures and supramolecular associations,” Polyhedron, vol. 14, no. 23–24, pp. 3389-3472, 1995.
• [18] I. Haiduc, D.B. Sowerby, “Stereochemical aspects of phosphor-1,1-dithiolato metal complexes: Coordination patterns, molecular structures and supramolecular associations in dithiophosphinates and related compounds,” Polyhedron, vol. 15, pp. 2469-2521, 1996.
• [19] I.P. Gray, H. L. Milton, A.M.Z. Slawin, J.D. Woollins, “Synthesis and structure of [Fc(RO)PS2]- complexes,” Dalton Trans., pp. 3450–3457, 2003.
• [20] M. Karakus, H. Yılmaz, , “Synthesis and Characterization of Ni(II), Zn(II), and Cd(II) Complexes with Dithiophosphonate Derivatives, ” Russian Journal of Coordination Chemistry, vol. 32, no. 6, pp. 437–443, 2006.
• [21] S. Blaurock, F.T. Edelmann, I. Haiduc, G. Mezei, P. Poremba, “Dimeric thiophosphorus complexes of sodium and zinc: Structural characterization of [(THF)2NaO(S)PPh2]2 and [Zn{S2P(OMe)C6H4OEt- p}2]2, ” Inorg. Chim. Acta, vol. 361, pp. 407–410, 2008.
• [22] I.P. Gray, A.M.Z. Slawin, J.D. Woollins, “Synthesis And Structure Of [An(RO)PS2]− Complexes” Dalton Trans., vol. 16, no. 24, pp. 2477-2486, 2004.
• [23] S. Sewpersad, W.E. Van Zyl, “Bis [μ-O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ2 S:S']bis{[O-isopropyl (4-ethoxyphenyl)dithiophosphonato-κ2 S,S']mercury(II)},” Acta Crystallographica, Section E, vol. E68, no. 12, pp. m1488-m1489, 2012.
• [24] E.G. Sağlam, E. Bulat, H. Yılmaz, “The Syntheses and Characterization of New Dithiophosphonates derived from Novel 2,4-Bis(methoxytolyl)-1,3-dithia-2,4-diphosphetane 2,4- disulfides and Their Ni(II) Complexes,” JOTCSA, vol. 7, no. 3, pp. 789-800, 2020.
• [25] E.G. Sağlam, E. Bulat, N. Acar, İ. Demirel, “New Homodinuclear Alkyl- and Aryl- Dithiophosphonato Cd(II) and Hg(II) complexes: Syntheses and Characterizations,” JOTCSA, vol. 7, no. 1, pp. 49-64, 2020.
• [26] M.C. Aragoni, M.Arca, F. Demartin, F.A. Devillanova, C. Graiff, F. Isaia, V. Lippolis, A.Tiripicchio, G. Verani, “Reactivity of phosphonodithioato NiII complexes: solution equilibria, solid state studies and theoretical calculations on the adduct formation with some pyridine derivatives,” J. Chem. Soc., Dalton Trans., pp.2671–2677, 2001.
• [27] M. Chakravarty, S. Pailloux, S. Ouizem, K.A. Smith, E.N. Duesler, R.T. Paine, N.J. Williams, R.D. Hancock, “Synthesis and metal coordination chemistry of (phenyl)(pyridine-2- ylmethyl)phosphinodithioic acid, [2-C5H4N]CH2P(S)(SH)(Ph),” Polyhedron, vol. 33, pp. 327-35, 2012.
• [28] S. Heinz, H. Keck, W.Kuchen,“Mass spectrometric studies of dithiophosphinato metal complexes,” Org. Mass Spectrom., vol. 19, pp. 82-86, 1984.
• [29] M. Karakuş, H. Yılmaz, “Synthesis and Characterization of Ni(II), Zn(II), and Cd(II) Complexes with Dithiophosphonate Derivatives,” Russ. J. Coord Chem, vol. 32, no. 6, pp. 437–43, 2006.
• [30] E.G. Sağlam, E. Bulat, C.T. Zeyrek, H. Dal, T. Hökelek,, “Syntheses of and structural studies on some square planar dithiophosphonato Ni(II) complexes, octahedral pyridine derivatives thereof and X- ray crystallography, DFT and molecular docking studies of the latter,” J. Mol. Struct., vol. 1178, pp. 112-125, 2019.
• [31] E.G. Sağlam, A. Ebinç, “Syntheses and Spectroscopic Characterization on New [O-3-phenyl-1- propyl-(4-methoxyphenyl)dithiophosphonato] Ni(II), Cd(II) and Hg(II) Complexes,” JOTCSA, vol. 5, no. 3, pp. 1239-1248, 2018.
• [32] E.G. Sağlam, N. Acar, “Syntheses and characterization of new dithiophosphinato zinc complexes,” JOTCSA, vol. 5, no. 2, pp. 931-940, 2018.
• [33] E.G. Sağlam, H. Dal, B.Mougang-Soume, T. Hökelek, “Syntheses and structural characterization of new trans-bis-[n-butyl- (p-methoxyphenyl) dithiophosphinato] nickel(II), the pyridine derivative thereof, and bis-{bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato]cobalt(II)} complexes, ” J. Mol. Struct., vol. 1202, 127222, 2020.