Palladium (II) Mixed Ligand Complexes of Benzoisothiazol-3(2H)-Dithiocarbamate (Bit-dtc) and Tertiary Diphosphines: Synthesis, Characterization, Biological and Anticancer Studies

Authors

  • Nazk Aziz Department of Chemistry, College of Science, University of Sulaimani, Sulaimaniyah, Iraq.

DOI:

https://doi.org/10.21123/bsj.2024.9491

Keywords:

Anticancer activity, Benzoisothiazol-3-dithiocarbamate, Mixed ligand complexes, Palladium, Phosphine.

Abstract

 [Pd(bit-dtc)2] complex was prepared by the reaction of sodium benzoisothiazol-3(2H)-dithiocarbamate (Nabit-dtc) with sodium tetrachloropalladate(II). Treatment of [Pd(bit-dtc)2] with one mole equivalent of Ph2P(CH)nPPh2 afforded complexes of the type [Pd(bit-dtc)2(Ph2(CH2)n PPh2)] in good yield : n=1(dppm); n=2 (dppe), n=3 (dppp); n=4 (dppb); n=(C5H4)2Fe (dppf). The prepared complexes were characterized by elemental analysis, I.R., 1H-{31P} and 31P-{1H} NMR spectroscopy the dithiocarbamate ligand bonded as mono dentate with Pd ion. The NMR spectroscopic data suggested that the prepared complexes have mononuclear coordination mode with diphosphines binding as chelating ligands, except dppm which behaves as bridging ligand, afforded binuclear complex. The antimicrobial activities of the newly synthesized Pd(II) complexes were evaluated against two types of bacteria, namely Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Furthermore, the complexes where n= 2, 4 and 5 were screened against pancreatic adenocarcinoma (SNU-2469), human gastric-esophageal adenocarcinoma (SK-GT-5), and healthy cell(WRL68). The complex [Pd(bit-dtc)2(dppe)] exhibited a significant activity against pancreatic adenocarcinoma of SNU-2469 cancer cells with IC50 value of 5.067 µM.

References

Bobinihi FF, Onwudiwe DC, Ekennia AC, Okpareke OC, Aderne C, Lane JR. Group 10 metal complexes of dithiocarbamates derived from primary anilines: Synthesis, characterization, computational and antimicrobial studies. Polyhedron. 2019 Jan 158: 296-310. https://doi.org/10.1016/j.poly.2018.10.073.

Muhammed RA, Abdullah BH, Rahman HS. Synthesis, cytotoxic, antibacterial, antioxidant activities, DFT, and docking of novel complexes of Palladium (II) containing a thiourea derivative and diphosphines. J. Mol. Struct. 2023 Jan 5;1295:136519. https://doi.org/10.1016/j.molstruc.2023.136519

Khan SZ, Rehman Z, Amir MK, Ullah I, Akhter MS, Gariepy FB. Heteroleptic Palladium(II) dithiocarbamates: Synthesis, characterization and in vitro biological screening. J Mol. Struct. 2018 Mar 15; 1156: 564-570. https://doi.org/10.1016/j.molstruc.2017.11.068.

Faihan AS, Hatshan MR, Alqahtani AS, Nasr FA, Al-Jibori SA, Al-Janabi AS. New divalent metal ion complexes with 1, 8-diaminonapthalene-2-thione: Synthesis, Spectroscopic, anti-bacterial and anticancer activity studies. J Mol Struct. 2022 Jan 5; 1247: 131291. https://doi.org/10.1016/j.molstruc.2021.131291

Faihan AS, Hatshan MR, Kadhim MM, Alqahtani AS, Nasr FA, Saleh AM, et al. Promising bio-active complexes of platinum (II) and palladium (II) derived from heterocyclic thiourea: Synthesis, characterization, DFT, molecular docking, and anti-cancer studies. J Mol Struct. 2022 Mar 15; 1252:132198. https://doi.org/10.1016/j.molstruc.2021.132198

Faihan AS, Al-Jibori SA, Al-Janabi AS. Novel base-free dianion complexes of Pt (II) and Pd (II) derived from heterocyclic thiourea and tertiary phosphine ligands. J Mol Struct. 2022 Mar 5; 1251: 131966. https://doi.org/10.1016/j.molstruc.2021.131966

Zvarych V, Stasevych M, Lunin V, Deniz NG, Sayil C, Ozyurek M, et al. Synthesis and investigation of antioxidant activity of the dithiocarbamate derivatives of 9, 10-anthracenedione. Monatsh Chem. 2016 Dec; 147: 2093-101. https://doi.org/10.1007/s00706-016-1839-y

Onwudiwe DC, Ekennia AC. Synthesis, characterization, thermal, antimicrobial and antioxidant studies of some transition metal dithiocarbamates. Res Chem Intermed. 2017 Mar; 43: 1465-85. https://doi.org/10.1007/s11164-016-2709-2

Choudhary A, Sharma R, Nagar M, Mohsin M, Meena HS. Synthesis, characterization and antioxidant activity of some transition metal complexes with terpenoid derivatives. J Chil Chem Soc. 2011 Dec; 56(4): 911-7. http://dx.doi.org/10.4067/S0717-97072011000400019

Amir MK, Rehman Z, Hayat F, Khan SZ, Hogarth G, Kondratyuk T, et al. Monofunctional platinum(II) dithiocarbamate complexes:Synthesis, characterization and anticancer activity. RSC Adv., 2016 Nov 6: 110517-110524. https://doi.org/10.1039/C6RA19469A

Al-Jibori SA, Gergees HM, Al-Rubaye MS, Modi SB, Ghosh S, Schmidt H, et al. Synthesis and molecular structures of palladium(II) metalated 2-phenylpyridine complexes [PdCl(pyC6H4)L] containing amino- or acetylamino-pyridine co-ligands. Inorg Chim Acta. 2016 Aug; 450: 50-56. https://doi.org/10.1016/j.ica.2016.04.046.

Khan MR, Zaib S, Khan A, Badshah A, Rauf MK, Din I, et al. Pd(II)-based heteroleptic complexes with N-(acyl)-N0, N0-(disubstituted)thioureas and phosphine ligands: Synthesis, characterization andcytotoxic studies against lung squamous, breast adenocarcinoma and Leishmania tropica. Inorg Chim Acta. 2018 Jul; 479: 189-196. https://doi.org/10.1016/j.ica.2018.04.060.

Mohamed DS, Al-Jibori SA, Ardakani RB, Faihan AS, Yousef TA, Alhamzani AG, et al. Spectroscopic, Anti-Cancer Activity, and DFT Computational Studies of Pt(II) Complexes with 1-Benzyl-3-phenylthiourea and Phosphine/Diamine Ligands. Inorganics. 2023 Mar ;11(3): 125. https://doi.org/10.3390/inorganics11030125.

Al-Jibori SA, Al-Janabi AS, Al-Sahan SW, Wagner C. Pd (II)-pyrrolidine dithiocarbamate complexes: Synthesis, spectroscopic studies and molecular structure of [Pd (PyDT)(ppy)]. J Mol Struct. 2021 Mar 5; 1227: 129524. https://doi.org/10.1016/j.molstruc.2020.129524.

Siddiqi KS, Nishat N. Synthesis and characterization of succinimide and phthalevhde dithiocarbamates and their complexes with some transition metal ions. Synth React Inorg met.-Org Chem. 2000 Sep 1; 30(8): 1505-18. https://doi.org/10.1080/00945710009351849.

Frei A, Zuegg J, Elliott AG, Baker M, Braese S, Brown C, et al. Metal complexes as a promising source for new antibiotics. Chem Sci., 2020 Feb; 11: 2637-2639. https://doi.org/10.1039/C9SC06460E.

Shaalan N. Preparation, Spectroscopy, Biological Activities and Thermodynamic Studies of New Complexes of Some Metal Ions with 2-[5-(2-Hydroxy-Phenyl)-1, 3, 4-Thiadiazol-2-Ylimino]-Methyl-Naphthalen-1-Ol]. Baghdad Sci J. 2022 Aug 1; 19(4): 0829-0837. http://dx.doi.org/10.21123/bsj.2022.19.4.0829

Mahmood WA, Aldabbagh AK, Mahmoud MA. Synthesis and Characterization of New Benzothiazole-derived Schiff Bases Metal Complexes. Baghdad Sci J. 2022 Apr 1; 19(2): 0378. http://dx.doi.org/10.21123/bsj.2022.19.2.0378.

Al-Janabi EMA, Hatshan MR, Adil SF, Kadhum WR, Al-Jibori SA, Faihan AS, et al. Spectroscopic, antibacterial and anti-cancer studies of new platinum(II)-diethyldithiocarbamate mixed ligand complexes with phosphine or amine ligands. J Mol Struct., 2022 Mar; 1252: 132227. https://doi.org/10.1016/j.molstruc.2021.132227.

Faihan AS, Al-Jibori SA, Hatshan MR, Al-Janabi AS. Antibacterial, spectroscopic and X-ray crystallography of newly prepared heterocyclic thiourea dianion platinum (II) complexes with tertiary phosphine ligands. Polyhedron. 2022 Jan 15; 212: 115602. https://doi.org/10.1016/j.poly.2021.115602.

Al‐Janabi AS, Al‐Samrai OA, Yousef TA. New palladium (II) complexes with 1‐phenyl‐1H‐tetrazole‐5‐thiol and diphosphine Synthesis, characterization, biological, theoretical calculations and molecular docking studies. Appl Organomet Chem. 2020 Dec; 34(12): e5967. https://doi.org/10.1002/aoc.5967

Lobana TS. Heterocyclic-2-thione derivatives of group 10–12 metals: Coordination versatility, activation of C=S (thione) bonds and biochemical potential. Coord Chem Rev. 2021 Aug; 441: 213884. https://doi.org/10.1016/j.ccr.2021.213884

Lobana TS, Kaur P, Hundal G, Butcher RJ, Liu CW. 1, 9-Dihydro-purine-6-thione Derivatives of the d8–d10 Metal Ions (PdII, PtII, and CuI): Synthesis, Spectroscopy, and Structures. Z Anorg Allg Chem. 2012 Sep ;638: 2340. https://doi.org/10.1002/zaac.201200278

Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds, part B: applications in coordination, organometallic, and bioinorganic chemistry. John Wiley & Sons; 6th. Ed. 2009 Jan 16: 1-221. https://doi.org/10.1002/9780470405840

Al-Jibori SA, Ulghafoor MA, Karadag A, Aydin A, Akbas H, Ruiz SG, Synthesis, characterization and anti-tumor activity of Pd(II) complexes with 4,5-benzo-3H-1,2-dithiole-3-thione. Transit Met Chem. 2019 Mar; 44: 575-583. https://doi.org/10.1007/s11243-019-00314-6.

Aziz NM, Abdullah BH. Synthesis, cytotoxicity, antibacterial activity and molecular modeling study of new mono, homo and heterobimetallic complexes of palladium (II) with some transition metal ions containing the ligands N-phenyl-N'-(2-thiazolyl) thiourea and Diphosphines Ph2P (CH2)nPPh2 (where n= 1–3). Indian J Chem. 2019; 58A: 772-782.

Al‐Janabi AS, Kadhim MM, Al‐Nassiry AI, Yousef TA. Antimicrobial, computational, and molecular docking studies of Zn (II) and Pd (II) complexes derived from piperidine dithiocarbamate. Appl. Organomet. Chem. 2021 Feb; 35(2): e 6108. https://doi.org/10.1002/aoc.6108.

Faihan AS, Aziz NM, Ashfaq M, Hassan WM, Al-Jibori SA, Al-Janabi AS. Synthesis, characterization, and x-ray crystallography of unexpected chloro-substitution on 1-(4-chlorophenyl)-3-phenylthiourea platinum (II) complex with tertiary phosphine ligand. J Mol Struct. 2022 Dec 15; 1270: 133985. https://doi.org/10.1016/j.molstruc.2022.133985

Rahman HS, Rasedee A, How CW, Abdul AB, Zeenathul NA, Othman HH, et al. Zerumbone-loaded nanostructured lipid carriers: preparation, characterization, and antileukemic effect. Int J Nanomed. 2013 Aug 2: 2769-2781. https://doi.org/10.2147/IJN.S45313.

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Palladium (II) Mixed Ligand Complexes of Benzoisothiazol-3(2H)-Dithiocarbamate (Bit-dtc) and Tertiary Diphosphines: Synthesis, Characterization, Biological and Anticancer Studies. Baghdad Sci.J [Internet]. [cited 2024 Dec. 21];22(3). Available from: https://bsj.uobaghdad.edu.iq/index.php/BSJ/article/view/9491