Synthesis, characterization and crystal structures of platinum(II) saccharinate complexes with 1,5-cyclooctadiene

Two new platinum(II) complexes, namely [PtCl(sac)(COD)] (1) and [Pt(sac) 2 (COD)] (2) (sac = saccharinate and COD = 1,5-cyclooctadiene), were synthesized and characterized by elemental analysis, IR, NMR, ESI-MSspectroscopic and thermal analysis (TG/DTA) methods. The platinum(II) complexes were prepared from the reactionof [$PtCl_2$ (COD)] with Na(sac)•$2H_2O$. The addition of the sac ligand resulted in the replacement of 1 and 2 chloridoligands in [PtCl 2 (COD)] to yield 1 and 2, respectively. The structures of the complexes were determined by singlecrystal X-ray diffraction and showed a distorted square planar coordination geometry around platinum(II). COD actedas a π -donor ligand, while sac was N -coordinated in both complexes. The TG/DTA data indicated that both complexeswere thermally stable up to 220 °C in air and their thermal decompositions yielded Pt as a final product. Complexes 1and 2 were also designed as possible precursors to synthesize new mixed-ligand platinum(II) sac complexes in a one-potreaction.

PDF

___

1. Rosenberg B, Van Camp L, Krigas T. Inhibition of cell division in Escherichia coli by electrolysis products from a platinum electrode. Nature 1965; 205: 698-699. doi: 10.1038/205698a0
2. Rosenberg B, Van Camp L, Trosko JE, Mansour VH. Platinum compounds: A new class of potent antitumour agents. Nature 1969; 222: 385-386. doi: 10.1038/222385a0
3. Rosenberg B. Some biological effects of platinum compounds: New agents for the control of tumours. Platinum Metals Review 1971; 15 (2): 42-51.
4. Drew D, Doyle JR. Cyclic diolefin complexes of platinum and palladium. Inorganic Syntheses 1990; 28: 346-349. doi: 10.1002/9780470132593.ch89
5. Otto S, Elding LI. Low temperature kinetic study of very fast substitution reactions at platinum(II) trans to olefins. Journal of the Chemical Society, Dalton Transactions 2002; 11: 2354-2360. doi: 10.1039/b200197g
6. Wandler AEE, Koos MRM, Nieger M, Luy B, Brase S. 1,5-Cyclooctadienyl alcohols and ketones generate a new class of COD Pt complexes. Dalton Transactions 2018; 47 (11): 3689-3692. doi: 10.1039/c8dt00075a
7. Durak LJ, Lewis JC. Transmetalation of alkyl ligands from Cp*(PMe 3)IrR1 R 2 to (cod)PtR3 X. Organometallics 2013; 32 (11): 3153-3156. doi: 10.1021/om400289s
8. Weliange NM, Sharp PR. Ethylene oxidation by a platinum(II) hydroxo complex. Insights into the wacker process. Organometallics 2012; 31 (19): 6823-6833. doi: 10.1021/om300626a
9. Jagadeesh MN, Thiel W. Hydrosilylation with bis(alkynyl) (1,5-cyclooctadiene)platinum catalysts: A density functional study of the initial activation. Organometallics 2002; 21 (10): 2076-2087. doi: 10.1021/om0200196
10. McCrindle R, Arsenault GJ, Farwaha R, Hampden-Smith MJ, McAlees AJ. A model for the polymerisation of diazomethane by transition metal complexes. Journal of Chemical Society, Chemical Communications 1986; 12: 943-944. doi: 10.1039/C39860000943
11. Cummings SD, Eisenberg R. Luminescent platinum(II) complexes of quinoxaIine-2,3-dithioIate. Inorganic Chemistry 1995; 34 (8): 2007-2014. doi: 10.1021/ic00112a010
12. Hierso J-C, Serp P, Feurer R, Kalck P. MOCVD of rhodium, palladium and platinum complexes on fluidized divided substrates: Novel process for one-step preparation of noble-metal catalysts. Applied Organometallic Chemistry 1998; 12 (3): 161-172. doi: 10.1002/(SICI)1099-0739(199803)12:3<161::AID-AOC689>3.0.CO;2-6
13. Lingen V, Lüning A, Krest A, Deacon GB, Schur J et al. Labile Pd-sulphur and Pt-sulphur bonds in organometallic palladium and platinum complexes [(COD)M(alkyl)(S-ligand)] n+ -A speciation study. Journal of Inorganic Biochemistry 2016; 165: 119-127. doi: 10.1016/j.jinorgbio.2016.06.009
14. Lüning A, Neugebauer M, Lingen V, Krest A, Stirnat K et al. Platinum diolefin complexes – Synthesis, structures, and cytotoxicity. European Journal of Inorganic Chemistry 2015; 2: 226-239. doi: 10.1002/ejic.201402954
15. Enders M, Görling B, Braun AB, Seltenreich JE, Reichenbach LF et al. Cytotoxicity and NMR studies of platinum complexes with cyclooctadiene ligands. Organometallics 2014; 33 (15): 4027-4034. doi: 10.1021/om500540x
16. Lüning A, Schur J, Hamel L, Ott I, Klein A. Strong cytotoxicity of organometallic platinum complexes with alkynyl ligands. Organometallics 2013; 32 (13): 3662-3672. doi: 10.1021/om400293u
17. Klein A, Lüning A, Ott I, Hamel L, Neugebauer M et al. Organometallic palladium and platinum complexes with strongly donating alkyl coligands–Synthesis, structures, chemical and cytotoxic properties. Journal of Organometallic Chemistry 2010; 695 (15-16): 1898-1905. doi: 10.1016/j.jorganchem.2010.04.027
18. Butsch K, Elmas S, Sen Gupta N, Gust R, Heinrich F et al. Organoplatinum(II) and -palladium(II) complexes of nucleobases and their derivatives. Organometallics 2009; 28 (13): 3906-3915. doi: 10.1021/om900208r
19. Klein A, Schurr T, Scherer H, Sen Gupta N. Cytosine binding in the novel organoplatinum(II) complex [(COD)PtMe (cytosine)](SbF6). Organometallics 2007; 26 (1): 230-233. doi: 10.1021/om060856y
20. Baran EJ, Yılmaz VT. Metal complexes of saccharin. Coordination Chemistry Reviews 2006; 250 (15-16): 1980- 1999. doi: 10.1016/j.ccr.2005.11.021
21. Ulukaya E, Arı F, Dimas K, Sarımahmut M, Güney E et al. Cell death-inducing effect of novel palladium(II) and platinum(II) complexes on non-small cell lung cancer cells in vitro. Journal of Cancer Research and Clinical Oncology 2011; 137 (10): 1425-1434. doi: 10.1007/s00432-011-1021-1
22. Güney E, Yılmaz VT, Arı F, Büyükgüngör O, Ulukaya E. Synthesis, characterization, structures and cytotoxic activity of palladium(II) and platinum(II) complexes containing bis(2-pyridylmethyl)amine and saccharinate. Polyhedron 2011; 30 (1): 114-122. doi: 10.1016/j.poly.2010.09.037
23. Arı F, Aztopal N, İçsel C, Yılmaz VT, Güney E et al. Synthesis, structural characterization and cell death-inducing effect of novel palladium(II) and platinum(II) saccharinate complexes with 2-(hydroxymethyl)pyridine and 2-(2- hydroxyethyl)pyridine on cancer cells in vitro. Bioorganic & Medicinal Chemistry 2013; 21 (21): 6427-6434. doi: 10.1016/j.bmc.2013.08.050
24. Cavicchioli M, Massabni AC, Castellano EE, Sabeh LPB, Costa-Neto CM. Synthesis and X-ray structure of the dinuclear platinum(II) complex with saccharin {K[Pt(sac) 3 (H2 O)] •H2 O} 2 : Studies on its antiproliferative activity in aqueous solution. Inorganica Chimica Acta 2007; 360 (9): 3055-3060. doi: 10.1016/j.ica.2007.02.040
25. Al-Jibori SA, Al-Jibori GH, Al-Hayaly LJ, Wagner C, Schmidt H et al. Combining anti-cancer drugs with artificial sweeteners: synthesis and anti-cancer activity of saccharinate (sac) and thiosaccharinate (tsac) complexes cis-[Pt(sac) 2 (NH3)2 ] and cis-[Pt(tsac) 2 (NH3)2 ]. Journal of Inorganic Biochemistry 2014; 141: 55-57. doi: 10.1016/j.jinorgbio.2014.07.017
26. Yılmaz VT, İçsel C, Turgut ÖR, Aygün M, Erkısa M et al. Synthesis, structures and anticancer potentials of platinum(II) saccharinate complexes of tertiary phosphines with phenyl and cyclohexyl groups targeting mitochondria and DNA. European Journal of Medicinal Chemistry 2018; 155: 609-622. doi: 10.1016/j.ejmech.2018.06.035
27. İçsel C, Yılmaz VT, Aygün M, Cevatemre B, Alper P et al. Palladium(II) and platinum(II) saccharinate complexes with bis(diphenylphosphino)methane/ethane: synthesis, S-phase arrest and ROS-mediated apoptosis in human colon cancer cells. Dalton Transactions 2018; 47 (33): 11397-11410. doi: 10.1039/C8DT02389A
28. Yılmaz VT, İçsel C, Aygün M, Erkısa M, Ulukaya E. Pd(II) and Pt(II) saccharinate complexes of bis(diphenylphosphi no)propane/butane: Synthesis, structure, antiproliferative activity and mechanism of action. European Journal of Medicinal Chemistry 2018; 158: 534-547. doi: 10.1016/j.ejmech.2018.09.035
29. İçsel C, Yılmaz VT, Cevatemre B, Aygün M, Ulukaya E. Structures and anticancer activity of chlorido platinum(II) saccharinate complexes with mono- and dialkylphenylphosphines. Journal of Inorganic Biochemistry 2019; 195: 39- 50. doi: 10.1016/j.jinorgbio.2019.03.008
30. Syed A, Stevens ED, Cruz SG. Reexamination of the π bonding in dichloro(cycloocta-1,5-diene)platinum. Inorganic Chemistry 1984; 23 (22): 3673-3674. doi: 10.1021/ic00190a053
31. Otto S. Structure and solution behaviour of cyclooctadiene complexes of platinum(II). Inorganica Chimica Acta 2010; 363 (13): 3316-3320. doi: 10.1016/j.ica.2010.06.020
32. Klein A, Klinkhammer K-W, Scheiring T. Cyclooctadienemethylplatinum complexes: synthesis, reactivity, molecular structure and spectroscopic properties of the organometallic hydroxoplatinum(II) complex [(COD)PtMe(OH)]. Journal of Organometallic Chemistry 1999; 592 (1): 128-135. doi: 10.1016/S0022-328X(99)00500-8
33. Henderson W, Nicholson BK, McCaffrey LJ. Platinum(II) and palladium(II) saccharinate complexes. Inorganica Chimica Acta 1999; 285 (1): 145-148. doi: 10.1016/S0020-1693(98)00327-2
34. Sheldrick GM. SHELXT–Integrated space-group and crystal structure determination. Acta Crystallographica Section A Foundations and Advances 2015; A71: 3-8. doi: 10.1107/S2053273314026370
35. Sheldrick GM. Crystal structure refinement with SHELXL. Acta Crystallographica Section C Structural Chemistry 2015; C71: 3-8. doi: 10.1107/S2053229614024218
36. Dolomanov OV, Bourhis LJ, Gildea RJ, Howard JAK, Puschmann H. OLEX2: a complete structure solution, refinement and analysis program. Journal of Applied Crystallography 2009; 42 (2): 339-341. doi: 10.1107/S0021889808042726