Synthesis, Spectral Characterization, Crystal Structure, and Antioxidant Properties of novel Palladium(II) Complex from ONS Donor 1,5-bis(2-hydroxybenzylidene)thiocarbohydrazone

Year 2023, , 129 - 138, 28.02.2023

Yeliz Kaya

https://doi.org/10.18596/jotcsa.1194323

Abstract

A new Pd(II) complex, [Pd(PPh3)(L)] (L = 1,5-bis(2-hydroxybenzylidene)thiocarbohydrazone, PPh3 = triphenylphosphine), was synthesized and characterized by FTIR, 1H NMR and UV-Vis spectroscopies and elemental analysis. The molecular structure of [Pd(PPh3)(L)] was confirmed by the single-crystal X-ray diffraction technique. Palladium ion has distorted square planar geometry according to X-ray diffraction studies. The free thiocarbohydrazone (L), potentially a pentadentate ONSNO donor, acted as a tridentate ONS donor. The antioxidant capacity of the free thiocarbohydrazone and Pd(II) complex was determined using the CUPRAC (cupric reducing antioxidant capacity) method. Also, the DPPH method was used to test the free radical scavenging activity of the free thiocarbohydrazone and Pd(II) complex. Antioxidant activity studies showed that free thiocarbohydrazone exhibited better activity than Pd(II) complex.

Keywords

Thiocarbohydrazone, Palladium(II) complex, Triphenylphosphine, Crystal structure, Antioxidant activity

Thanks

I dedicate this paper to Prof. Dr. Ayşe ERÇAĞ, the mentor of my research career.

References

• 1. El-Mahdy KM, El-Kazak AM, Abdel-Megid M, Seada M, Farouk O. of Some New Heterocyclic Schiff Bases Derived from Thiocarbohydrazide. ACSi. 2016 Mar 15;63(1):18–25.
• 2. Mamatha GP, Sherigara BS, Mahadevan KM. Electrooxidation of carbo/thiocarbohydrazide and their hydrazone derivatives at a glassy carbon electrode. J Chem Sci. 2007 May;119(3):267–74.
• 3. Kurzer F, Wilkinson M. Chemistry of carbohydrazide and thiocarbohydrazide. Chemical Reviews. 1970;70(1):111–49.
• 4. Metwally MA, Khalifa ME, Koketsu M. Thiocarbohydrazides: Synthesis and reactions. American Journal of Chemistry. 2012;2(2):38–51.
• 5. Bonaccorso C, Marzo T, La Mendola D. Biological Applications of Thiocarbohydrazones and Their Metal Complexes: A Perspective Review. Pharmaceuticals. 2019 Dec 25;13(1):4.
• 6. Nalawade A, Nalawade R, Londhe B, Tarwal N, Shejwal R. Microwave assisted synthesis, structure, spectral characterization and biological studies of (e)-n’-(4-fluoro benzylidene) hydrazinecarbothiohydrazide. International Journal of Pharmaceutical Science Invention. 2015;4(5):1–4.
• 7. Zafarian H, Sedaghat T, Motamedi H, Amiri Rudbari H. A multiprotic ditopic thiocarbohydrazone ligand in the formation of mono- and di-nuclear organotin(IV) complexes: Crystal structure, antibacterial activity and DNA cleavage. Journal of Organometallic Chemistry. 2016 Dec;825–826:25–32.
• 8. Singh DP, Kumar K, Chopra RM ne’e. Spectroscopic studies and antibacterial activities of some new 16-membered octaazamacrocyclic complexes derived from thiocarbohydrazide and pentane-2,4-dione. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2011 Feb;78(2):629–34.
• 9. Melha KSA. In-vitro antibacterial, antifungal activity of some transition metal complexes of thiosemicarbazone Schiff base (HL) derived from N 4 -(7′-chloroquinolin-4′-ylamino) thiosemicarbazide. Journal of Enzyme Inhibition and Medicinal Chemistry. 2008 Jan 1;23(4):493–503.
• 10. Parsekar SU, Paliwal K, Haldar P, Antharjanam PKS, Kumar M. Synthesis, Characterization, Crystal Structure, DNA and HSA Interactions, and Anticancer Activity of a Mononuclear Cu(II) Complex with a Schiff Base Ligand Containing a Thiadiazoline Moiety. ACS Omega. 2022 Jan 25;7(3):2881–96.
• 11. Ibrahim AA, Kareem MM, Al-Noor TH, Al-Muhimeed T, AlObaid AA, Albukhaty S, et al. Pt(II)-Thiocarbohydrazone Complex as Cytotoxic Agent and Apoptosis Inducer in Caov-3 and HT-29 Cells through the P53 and Caspase-8 Pathways. Pharmaceuticals. 2021 May 26;14(6):509.
• 12. Muğlu H, Kurt BZ, Sönmez F, Güzel E, Çavuş MS, Yakan H. Preparation, antioxidant activity, and theoretical studies on the relationship between antioxidant and electronic properties of bis(thio/carbohydrazone) derivatives. Journal of Physics and Chemistry of Solids. 2022 May;164:110618.
• 13. Kaya Y, Erçağ A, Koca A. New square-planar nickel(II)-triphenylphosphine complexes containing ONS donor ligands: Synthesis, characterization, electrochemical and antioxidant properties. Journal of Molecular Structure. 2020 Apr;1206:127653.
• 14. Kaya Y, Erçağ A, Uğuz Ö, Koca A, Zorlu Y, Hacıoğlu M, et al. New asymmetric bisthiocarbohydrazones and their mixed ligand nickel(II) complexes: Synthesis, characterization, crystal structure, electrochemical-spectroelectrochemical property, antimicrobial and antioxidant activity. Polyhedron. 2021 Oct;207:115372.
• 15. Abbas SY, Farag AA, Ammar YA, Atrees AA, Mohamed AF, El-Henawy AA. Synthesis, characterization, and antiviral activity of novel fluorinated isatin derivatives. Monatsh Chem. 2013 Nov;144(11):1725–33.
• 16. Srividya L, Reddy A, Rama N. Antidiabetic activity of 1-(4-chlorobenzylidene)-5-(2-oxoindolin-3-ylidene) thiocarbohydrazone in chick model. Asian J Biol Sci. 2017;10:126–30.
• 17. Tejasree Ch, Kiran G, Rajyalakshmi G, Rama Narsimha Reddy A. Hepatoprotective activity of 1-(4-(Dimethylamino)Benzylidene)-5-(2-Oxoindolin-3-ylidene) Thiocarbohydrazone in rats. Toxicological & Environmental Chemistry. 2013 Oct;95(9):1589–94.
• 18. Sadlapurkar AV, Barache UB, Shaikh AB, Gaikwad SH, Lokhande TN. 2-chlorobenzaldehyde thiocarbohydrazone: a novel reagent for liquid-liquid extractive spectrophotometric determination of copper(II) from environmental and real samples. International Journal of Environmental Analytical Chemistry. 2021 Apr 13;1–21.
• 19. Nalawade AM, Nalawade RA, Shejwal RV, Kamble GS, Ling YC, Anuse MA. Development of a reliable analytical method for the precise extractive spectrophotometric determination of cadmium(II) by using of chromogenic reagent: analysis of real samples. International Journal of Environmental Analytical Chemistry. 2022 Dec 16;102(16):4158–77.
• 20. Sadlapurkar AV, Barache UB, Shaikh AB, Dhale PC, Gaikwad SH, Lokhande TN. Statistically designed extractive spectrophotometric determination scheme for bismuth(III) with 2-chlorobenzaldehyde thiocarbohydrazone: Analysis of environmental and real resources. Chemical Data Collections. 2022 Feb;37:100798. Availabe from: <URL>.
• 21. Güveli Ş, Agopcan Çınar S, Karahan Ö, Aviyente V, Ülküseven B. Nickel(II)–PPh 3 Complexes of S , N ‐Substituted Thiosemicarbazones – Structure, DFT Study, and Catalytic Efficiency. Eur J Inorg Chem. 2016 Feb;2016(4):538–44.
• 22. Priyarega S, Kalaivani P, Prabhakaran R, Hashimoto T, Endo A, Natarajan K. Nickel(II) complexes containing thiosemicarbazone and triphenylphosphine: Synthesis, spectroscopy, crystallography and catalytic activity. Journal of Molecular Structure. 2011 Sep;1002(1–3):58–62.
• 23. Shabbir M, Akhter Z, Ashraf AR, Ismail H, Habib A, Mirza B. Nickel(II) and palladium(II) triphenylphosphine complexes incorporating tridentate Schiff base ligands: Synthesis, characterization and biocidal activities. Journal of Molecular Structure. 2017 Dec;1149:720–6.
• 24. Rohlík Z, Holzhauser P, Kotek J, Rudovský J, Němec I, Hermann P, et al. Synthesis and coordination properties of palladium(II) and platinum(II) complexes with phosphonated triphenylphosphine derivatives. Journal of Organometallic Chemistry. 2006 May;691(11):2409–23. Available from: 10.1016/j.jorganchem.2006.01.024.
• 25. Tan CP, Lu YY, Ji LN, Mao ZW. Metallomics insights into the programmed cell death induced by metal-based anticancer compounds. Metallomics. 2014;6(5):978.
• 26. Elsayed SA, Badr HE, di Biase A, El-Hendawy AM. Synthesis, characterization of ruthenium(II), nickel(II), palladium(II), and platinum(II) triphenylphosphine-based complexes bearing an ONS-donor chelating agent: Interaction with biomolecules, antioxidant, in vitro cytotoxic, apoptotic activity and cell cycle analysis. Journal of Inorganic Biochemistry. 2021 Oct;223:111549.
• 27. Anu D, Naveen P, Devendhiran T, Shyamsivappan S, Kumarasamy K, Lin MC, et al. Synthesis, spectral characterization, X-ray crystallography and biological evaluations of Pd(II) complexes containing 4(N)-substituted thiosemicarbazone. Journal of Coordination Chemistry. 2021 Dec 17;74(21–24):3153–69.
• 28. Nadeem S, Bolte M, Ahmad S, Fazeelat T, Tirmizi SA, Rauf MK, et al. Synthesis, crystal structures and, antibacterial and antiproliferative activities in vitro of palladium(II) complexes of triphenylphosphine and thioamides. Inorganica Chimica Acta. 2010 Oct;363(13):3261–9.
• 29. Shanmugapriya A, Jain R, Sabarinathan D, Kalaiarasi G, Dallemer F, Prabhakaran R. Structurally different mono-, bi- and trinuclear Pd( ii ) complexes and their DNA/protein interaction, DNA cleavage, and anti-oxidant, anti-microbial and cytotoxic studies. New J Chem. 2017;41(18):10324–38.
• 30. Ayyannan G, Mohanraj M, Gopiraman M, Uthayamalar R, Raja G, Bhuvanesh N, et al. New Palladium(II) complexes with ONO chelated hydrazone ligand: Synthesis, characterization, DNA/BSA interaction, antioxidant and cytotoxicity. Inorganica Chimica Acta. 2020 Nov;512:119868.
• 31. Khan H, Badshah A, Said M, Murtaza G, Sirajuddin M, Ahmad J, et al. Synthesis, structural characterization and biological screening of heteroleptic palladium(II) complexes. Inorganica Chimica Acta. 2016 Jun;447:176–82.
• 32. Kavitha P, Laxma Reddy K. Pd(II) complexes bearing chromone based Schiff bases: Synthesis, characterisation and biological activity studies. Arabian Journal of Chemistry. 2016 Sep;9(5):640–8.
• 33. Boubakri L, Mansour L, Harrath AH, Özdemir I, Yaşar S, Hamdi N. N-Heterocyclic carbene-Pd(II)-PPh 3 complexes as a new highly efficient catalyst system for the Sonogashira cross-coupling reaction: Synthesis, characterization and biological activities. Journal of Coordination Chemistry. 2018 Jan 17;71(2):183–99.
• 34. Bahl A, Grahn W, Stadler S, Feiner F, Bourhill G, Bräuchle C, et al. Novel, Blue-Transparent Frequency Doublers Based on 1,8-Di(hetero)arylnaphthalenes. Angew Chem Int Ed Engl. 1995 Jul 31;34(1314):1485–8.
• 35. Goldfinger MB, Crawford KB, Swager TM. Directed Electrophilic Cyclizations: Efficient Methodology for the Synthesis of Fused Polycyclic Aromatics. J Am Chem Soc. 1997 May 1;119(20):4578–93.
• 36. Hartwig JF, Kawatsura M, Hauck SI, Shaughnessy KH, Alcazar-Roman LM. Room-Temperature Palladium-Catalyzed Amination of Aryl Bromides and Chlorides and Extended Scope of Aromatic C−N Bond Formation with a Commercial Ligand. J Org Chem. 1999 Jul 1;64(15):5575–80.
• 37. Asma M, Badshah A, Ali S, Sohail M, Fettouhi M, Ahmad S, et al. Synthesis, Characterization of Mixed Ligand Palladium(II) Complexes of Triphenylphosphine and Anilines and their Enzyme Inhibition Studies against β-glucuronidase. The Crystal Structure of trans-dichloro-(m-chloroaniline)(triphenylphosphine)palladium(II). Transition Met Chem. 2006 May;31(4):556–9.
• 38. Shabbir M, Akhter Z, Ahmad I, Ahmed S, Shafiq M, Mirza B, et al. Schiff base triphenylphosphine palladium (II) complexes: Synthesis, structural elucidation, electrochemical and biological evaluation. Journal of Molecular Structure. 2016 Aug;1118:250–8.
• 39. Rocha FV, Barra CV, Garrido SS, Manente FA, Carlos IZ, Ellena J, et al. Cationic Pd(II) complexes acting as topoisomerase II inhibitors: Synthesis, characterization, DNA interaction and cytotoxicity. Journal of Inorganic Biochemistry. 2016 Jun;159:165–8.
• 40. Ahmed M, Khan SZ, Sher N, Rehman ZU, Mushtaq N, Khan RA. Kinetic and toxicological effects of synthesized palladium(II) complex on snake venom (Bungarus sindanus) acetylcholinesterase. J Venom Anim Toxins incl Trop Dis [Internet]. 2021 [cited 2023 Feb 8];
• 41. Kaya Y, Erçağ A, Zorlu Y, Demir Y, Gülçin İ. New Pd(II) complexes of the bisthiocarbohydrazones derived from isatin and disubstituted salicylaldehydes: Synthesis, characterization, crystal structures and inhibitory properties against some metabolic enzymes. J Biol Inorg Chem. 2022 Mar;27(2):271–81.
• 42. Ibrahim AA, Khaledi H, Ali HM. A multiprotic indole-based thiocarbohydrazone in the formation of mono-, di- and hexa-nuclear metal complexes. Polyhedron. 2014 Oct;81:457–64.
• 43. Burns GR. Metal complexes of thiocarbohydrazide. Inorganic Chemistry. 1968;7(2):277–83.
• 44. Kaya İ, Temizkan K, Kaya Y, Erçağ A. The monomers and polymers of azomethine-based thiocarbohydrazones: Fluorescent activities, fluorescence quantum yields of polymers in water and DMF solutions. Materials Science and Engineering: B. 2022 Aug;282:115782.
• 45. Bruker. APEX2, version 201411-0, Bruker. Bruker, AXS Inc, Madison, Wı; 2014.
• 46. Bruker. SAINT, version 834 A, Bruker. Bruker AXS Inc, Madison, WI; 2013.
• 47. Sheldrick GM. SHELXT – Integrated space-group and crystal-structure determination. Acta Crystallogr A Found Adv. 2015 Jan 1;71(1):3–8.
• 48. Sheldrick GM. Crystal structure refinement with SHELXL. Acta Crystallogr C Struct Chem. 2015 Jan 1;71(1):3–8.
• 49. Macrae CF, Sovago I, Cottrell SJ, Galek PTA, McCabe P, Pidcock E, et al. Mercury 4.0 : from visualization to analysis, design and prediction. J Appl Crystallogr. 2020 Feb 1;53(1):226–35.
• 50. Sánchez-Moreno C, Larrauri JA, Saura-Calixto F. A procedure to measure the antiradical efficiency of polyphenols. J Sci Food Agric. 1998 Feb;76(2):270–6.
• 51. Apak R, Güçlü K, Özyürek M, Karademir SE. Novel Total Antioxidant Capacity Index for Dietary Polyphenols and Vitamins C and E, Using Their Cupric Ion Reducing Capability in the Presence of Neocuproine: CUPRAC Method. J Agric Food Chem. 2004 Dec 1;52(26):7970–81.
• 52. Yanping R, Rongbin D, Liufang W, Jigui W. Synthesis, Characterization and Crystal Structure of 1,5-Bis(2-Hydroxybenzaldehyde)-Dithiocarbohydrazone. Synthetic Communications. 1999 Feb;29(4):613–7.
• 53. Lugasi SO. New synthetic pathways for thiocarbohydrazide and salicylaldehyde azine compounds.
• 54. Kaya Y, Erçağ A, Koca A. Synthesis, structures, electrochemical studies and antioxidant activities of cis-dioxomolybdenum(VI) complexes of the new bisthiocarbohydrazones. Journal of Molecular Structure. 2015 Dec;1102:117–26.
• 55. Özerkan D, Ertik O, Kaya B, Kuruca SE, Yanardag R, Ülküseven B. Novel palladium (II) complexes with tetradentate thiosemicarbazones. Synthesis, characterization, in vitro cytotoxicity and xanthine oxidase inhibition. Invest New Drugs. 2019 Dec;37(6):1187–97.
• 56. Manna CK, Naskar R, Bera B, Das A, Mondal TK. A new palladium(II) phosphino complex with ONS donor Schiff base ligand: Synthesis, characterization and catalytic activity towards Suzuki-Miyaura cross-coupling reaction. Journal of Molecular Structure. 2021 Aug;1237:130322.
• 57. Takjoo R, Takjoo R, Yazdanbakhsh M, Aghaei kaju A, Chen Y. Mixed Ligand Palladium(II) Complex with NS-Bidentate S -Allyldithiocarbazate Schiff Base: Synthesis, Spectral Characterization, Crystal Structure and Decoding Intermolecular Interactions with Hirshfeld Surface Analysis. Chin J Chem. 2010 Feb;28(2):221–8.
• 58. Apak R, Güçlü K, Özyürek M, Celik SE. Mechanism of antioxidant capacity assays and the CUPRAC (cupric ion reducing antioxidant capacity) assay. Microchimica Acta. 2008;160(4).
• 59. Asha TM, Prathapachandra Kurup MR. An insight into the potent antioxidant activity of a dithiocarbohydrazone appended cis ‐dioxidomolybdenum (VI) complexes. Appl Organomet Chem [Internet]. 2020 Sep [cited 2023 Feb 8];34(9).