Synthesis, Characterization, Catalytic Properties and Thermal Studies of ONO Type Schiff Base Complexes

Abstract

Some metal complexes were synthesized from Schiff base derived from 5-chloro-2-hydroxyacethophenone and N-aminopyrimidine-2-one. All compounds were characterized by elemental analyses, molar conductivity and magnetic measurements, IR, UV-Vis, Mass and NMR (for Pd (II)) spectral and analytic techniques. While Pd(II) complex displayed square planar geometry, the others exhibited octahedral geometry. The whole complexes showed non-electrolytic behavior. While Cu(II) and Co(II) complexes exhibited partial antiferromagnetic properties, Pd(II) complex showed diamagnetic property. Schiff base compound and new synthesized its some complexes were evaluated for cyclohexane oxidation under microwave irradiation. Both the microwave power and the novel catalysts were found to affect the selective oxidation of cyclohexane (CyH) to cyclohexanone (Cy = O) and cyclohexanol (Cy-OH). Cu(II) and Co(II) complexes were found to be more active in the reaction of the oxidation of cyclohexane than in the ligand and other complexes.

Keywords

• ONO type Schiff base complexes
• N-aminopyrimidine-2-one
• 5-chloro-2-hydroxyacethophenone
• Catalytic properties

ONO Tip Schiff Baz Komplekslerinin Sentezi, Karakterizasyonu, Katalitik Özellikleri ve Termal Çalışmaları

Abstract

5-kloro-2-hidroksiasetofenon ve 1-Amino-5-Benzoil-4-fenil-1H-pirimidin-2-on’dan (N-aminopirimidin-2-on) türeyen Schiff bazının bazı metal kompleksleri sentezlenmiştir. Bütün bileşikler elementel analiz, molar iletkenlik, manyetik moment ölçümü, IR, UV-Vis, kütle ve NMR (sadece Pd(II)) gibi spektral ve analitik tekniklerle karakterize edilmiştir. Pd(II) kompleksi kare düzlem geometriye sahipken, diğer kompleksler oktahedral yapıya sahiptir. Kompleksler iletkenlik özelliğine sahip değildir. Cu(II) ve Co(II) kompleksleri kısmi antiferromanyetik özellik gösterirken, Pd(II) kompleksi diyamanyetik özelliktedir. Schiff baz bileşiği ve yeni sentezlenen kompleksleri mikrodalga ışını altında siklohekzan oksidasyonu için incelenmiştir. Hem mikrodalga gücü hem de yeni katalizörlerin siklohekzanın (CyH) siklohekzanon (Cy=O) ve siklohekzanole (Cy–OH) seçici yükseltgenmesini etkilediği görülmüştür. Cu(II) ve Co(II) komplekslerinin liganda ve diğer komplekslere oranla siklohekzanın oksidasyonu reaksiyonunda daha aktif oldukları bulunmuştur.

Keywords

• ONO tip Schiff baz kompleks
• N-aminopirimidin-2-on
• 5-kloro-2-hidroksiasetofenon
• Katalitik özellik

References

1. [1] Kalita, M., Gogoi, P., Barman, P., Sarma, B., Buragohain, A. K., Kalita, R. D. 2014. A new series of Ni (II), Cu (II), Co (II) and Pd (II) complexes with an ONS donor Schiff base: Synthesis, crystal structure, catalytic properties and bioactivities. Polyhedron, 74(2014), 93-98.
2. [2] Khorshidifard, M., Rudbari, H. A., Askari, B., Sahihi, M., Farsani, M. R., Jalilian, F., Bruno, G. 2015. Cobalt (II), copper (II), zinc (II) and palladium (II) Schiff base complexes: Synthesis, characterization and catalytic performance in selective oxidation of sulfides using hydrogen peroxide under solvent-free conditions. Polyhedron, 95(2015), 1-13.
3. [3] Bazarganipour, M., Salavati-Niasari, M. 2015. Grafting of copper(II) Schiff base complex on functionalized multi-wall carbon nanotubes: Synthesis, characterization and catalytic aziridination of olefins. Appl Catal A Gen, 502(2015), 57-64.
4. [4] Anitha, P., Manikandan, R., Vijayan, P., Prakash, G., Viswanathamurthi, P., Butcher, R.-J. 2015. Nickel(II) complexes containing ONS donor ligands: Synthesis, characterization, crystal structure and catalytic application towards C-C cross-coupling reactions. J Chem Sci, 127(2015), 597-608.
5. [5] Reddy, P. A. N., Datta, R., Chakravarty, A. R. 2000. Synthesis, X-ray structure and catalytic properties of a copper(II) Schiff base complex modeling the activity of the CuB site of dopamine β-hydroxylase. Inorg Chem Commun, 3(2000), 322-324.
6. [6] Dolaz, M., McKee, V., Uruş, S., Demir, N., Sabik, A. E., Gölcü, A., Tümer, M. 2010. Synthesis, structural characterization, catalytic, thermal and electrochemical investigations of bidentate Schiff base ligand and its metal complexes. Spectrochim Acta Part A, 76(2010), 174-181.
7. [7] Tong, J., Li, Z., Xia, C. 2005. Highly efficient catalysts of chitosan-Schiff base Co(II) and Pd(II) complexes for aerobic oxidation of cyclohexane in the absence of reductants and solvents. J Mol Catal A Chem, 231(2005), 197-203.
8. [8] Fukuda, T., Katsuki, T. 1997. Highly enantioselective cyclopropanation of styrene derivatives using Co(III)-salen complex as a catalyst. Tetrahedron, 53(1997), 7201-7208.

9. [9] Masterson, D. S., Shirley, C., Glatzhofer, D. T. 2012. N-(4-[2.2]paracyclophanyl)-2′-hydroxyacetophenone imine: An effective paracyclophane Schiff-base ligand for use in catalytic asymmetric cyclopropanation reactions. J Mol Catal A Chem, 361-362(2012), 111-115.
10. [10] Genet, J. P., Juge, S., Achi, S., Mallart, S., Montes, J. R., Levif, G. 1988. Synthesis of α-amino acids using transition metal catalysis - alkylation of schiff bases derived from α-amimo acid esters (regio, stereo - selectivity). Tetrahedron, 44(1988), 5263-5275.
11. [11] Soğukömeroğulları, H. G., Taşkın Tok, T., Yılmaz, F., Berber, İ., Sönmez, M. 2015. Synthesis, characterization, biological studies, and molecular modeling of mixed ligand bivalent metal complexes of Schiff bases based on N-aminopyrimidine–2-one/2-thione. Turk J Chem, 39(2015), 497-509.
12. [12] Sönmez, M., Sogukomerogullari, H. G, Öztemel, F., Berber, İ. 2014. Synthesis and biological evaluation of a novel ONS tridentate Schiff base bearing pyrimidine ring and some metal complexes. Med Chem Res, 23(2014), 3451-3457.
13. [13] Akçamur, Y., Altural, B., Sarıpınar, E., Kollenz, G., Kappe, O., Peters, K., Peters, E., Schering, H. 1988. A convenient synthesis of functionalized 1H‐pyrimidine‐2‐thiones. J Heterocyclic Chem, 25(1988), 1419-1422.
14. [14] Akçamur, Y., Altural, B., Sarıpınar, E., Kollenz, G. 1989. A Simple Synthesis of Functionalized 1H-Pyrimidines.Reaction of Cyclic Oxalyl Compound. Monats für Chem, 120(1989), 1015-1020.
15. [15] Ceyhan, G., Çelik, C., Uruş, S., Demirtaş, İ., Elmastaş, M., Tümer, M. 2011. Antioxidant, electrochemical, thermal, antimicrobial and alkane oxidation properties of tridentate Schiff base ligands and their metal complexes. Spectrochim Acta Part A, 81(2011), 184-198.
16. [16] Emara, A. A. A., El-Sayed, B. A., Ahmed. E. A. E. 2008. Syntheses, spectroscopic characterization and thermal behavior on novelbinuclear transition metal complexes of hydrazones derived from4,6-diacetylresorcinol and oxalyldihydrazine. Spectrochim Acta Part A, 69(2008), 757-769.
17. [17] Sönmez, M., Şekerci, M. 2007. The template synthesis, spectral characterization and thermal behavior of new binuclear Schiff base complexes derived from N-aminopyrimidine with 2, 3-butandion. J Serb Chem Soc, 72(2007), 259-264.
18. [18] Belal, A. A. M., El-Deen, I. M., Farid, N. Y., Zakaria, R., Refat, M. S. 2015. Synthesis, spectroscopic, coordination and biological activities of some transition metal complexes containing ONO tridentate Schiff base ligand, Spectrochim Acta Part A, 149(2015), 771-787.
19. [19] Sönmez, M., Berber, İ., Akbaş, E. 2006. Synthesis, antibacterial and antifungal activity of some new pyridazinone metal complexes. Eur J Med Chem, 41(2006), 101-105.
20. [20] Önal, Z., Altural, B. 1999. Reactions of N-Amino-pyrimidine Derivatives, with 1,3-Dicarbonyl Compounds. Turk J Chem, 23(1999), 401-405.
21. [21] Abd-Elzaher, M. M. 2001. Spectroscopic characterization of some tetradentate Schiff bases and their complexes with nickel, copper and zinc. J Chin Chem Soc, 48(2001), 153-158.
22. [22] Gülcan, M., Sönmez, M. Berber, İ. 2012. Synthesis, characterization, and antimicrobial activity of a new pyrimidine Schiff base and its Cu (II), Ni (II), Co (II), Pt (II), and Pd (II) complexes. Turk J Chem, 36(2012), 189-200.
23. [23] Sönmez, M., Şekerci, M. Synthesis, Characterization and Thermal Investigation of Copper (II), Nickel (II), Cobalt (II) and Zinc (II) Complexes with 5‐Benzoyl‐1‐(phenylmethylenamino)‐4‐phenyl‐1H‐pyrimidine‐2‐thione. Synth React Inorg Met-Org Chem, 33(2003), 1689-1700.
24. [24] Sönmez, M., Çelebi, M. Berber, İ. 2010. Synthesis, spectroscopic and biological studies on the new symmetric Schiff base derived from 2, 6-diformyl-4-methylphenol with N-aminopyrimidine. Eur J Med Chem, 45(2010), 1935-1940.
25. [25] Tümer, M., Deligönül, N., Gölcü, A., Akgün, E., Dolaz, M., Demirelli, H., Dığrak, M. 2006. Mixed-ligand Copper (II) Complexes: Investigation of their Spectroscopic, Catalysis, Antimicrobial and Potentiometric Properties. Trans Met Chem, 31(2006), 1-12.
26. [26] Ray, S., Konar, S., Jana, A., Das, K., Dhara, A., Chatterjee, S., Kar, S. K. 2014. Syntheses, crystal structure, spectroscopic and photoluminescence studies of mononuclear copper(II), manganese(II), cadmium(II), and a 1D polymeric Cu(II) complexes with a pyrimidine derived Schiff base ligand. J Mol Struct, 1058(2014), 213-220.
27. [27] Gülcan, M., Sönmez, M. 2011. Synthesis and characterization of Cu (II), Ni (II), Co (II), Mn (II), and Cd (II) transition metal complexes of tridentate schiff base derived from o-vanillin and N-aminopyrimidine-2-thione. Phosphorus Sulfur and Silicon, 186(2011), 1962-1971.
28. [28] Ekmekcioglu, P., Karabocek, N., Karabocek, S., Emirik, M. 2015. Synthesis, structural and biochemical activity studies of a new hexadentate Schiff base ligand and its Cu(II), Ni(II), and Co(II) complexes. J Mol Struct, 1099(2015), 189-196.
29. [29] Modi, C. K. 2009. Synthesis, spectral investigation and thermal aspects of coordination polymeric chain assemblies of some transition metal ions with bis-pyrazolones. Spectrochim Acta Part A, 71(2009), 1741-1748.
30. [30] Tyagi, P., Chandra, S., Saraswat, B. S. Sharma, D. Design, spectral characterization, DFT and biological studies of transition metal complexes of Schiff base derived from 2-aminobenzamide, pyrrole and furan aldehyde. Spectrochim. Acta Part A, 143(2015), 1-11.
31. [31] Baran, T., Açıksöz, E., Mentes, A. 2015. Carboxymethyl chitosan Schiff base supported heterogeneous palladium (II) catalysts for Suzuki cross-coupling reaction. J Mol Catal A Chem, 407(2015), 47-52.
32. [32] Tümer, M., Köksal, H., Serin, S. 1998. Synthesis, Characterization and Thermal Investigation of Some Metal Complexes Derived from New Schiff Base Ligands. Synth React Inorg Met-Org Chem, 28(1998), 1393-1404.
33. [33] Sönmez, M., Çelebi, M., Levent, A., Berber, İ., Şentürk, Z. 2010. A new pyrimidine-derived ligand, N-pyrimidine oxalamic acid, and its Cu (II), Co (II), Mn (II), Ni (II), Zn (II), Cd (II), and Pd (II) complexes: synthesis, characterization, electrochemical properties, and biological activity. J Coord Chem, 63(2010), 848-860.
34. [34] Urus, S., Dolaz, M., Tümer, M. 2010. Synthesis and Catalytic Activities of Silica-Supported Multifunctional Azo-Containing Schiff Base Complexes with Cu(II), Co(II), Ni(II) and Mn(II). J Inorg Organomet Polym, 20(2010), 706-713.
35. [35] Retcher, B., Costa, J. S., Tang, J., Hage, R., Gamez, P., Reedijk, J. 2008. Unexpected high oxidation of cyclohexane by Fe salts and dihydrogen peroxide in acetonitrile. J Mol Catal A Chem, 286(2008), 1-5.
36. [36] Luque, R., Badamali, S. K., Clark, J. H., Fleming, M., Macquarrie, D. J. 2008. Controlling selectivity in catalysis: Selective greener oxidation of cyclohexene under microwave conditions. Appl Catal A Gen, 341(2008), 154-159.