Synthesis, Spectroscopic and Computational Studies of Some Metals Chelates with Chromene-2-one and Pyrazine-Based Ligands

Taghreed Mohy Al-Deen Musa; Mahmoud Najim Abid Aljibouri; Bayader Fadhil Abbas; Nahid Hasani

doi:10.22146/ijc.43857

Synthesis, Spectroscopic and Computational Studies of Some Metals Chelates with Chromene-2-one and Pyrazine-Based Ligands

https://doi.org/10.22146/ijc.43857

Taghreed Mohy Al-Deen Musa⁽¹⁾, Mahmoud Najim Abid Aljibouri^(2*), Bayader Fadhil Abbas⁽³⁾, Nahid Hasani⁽⁴⁾

(1) Department of Chemistry, College of Science, Mustansiriyah University, Baghdad, Iraq
(2) Department of Chemistry, College of Science, Mustansiriyah University, Baghdad, Iraq
(3) Department of Chemistry, College of Science, Mustansiriyah University, Baghdad, Iraq
(4) Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
(*) Corresponding Author

Abstract

The present paper deals with the synthesis of cobalt(II), nickel(II), copper(II) and cadmium(II) complexes with two bidentate ligands, L¹ (3-(quinoxaline-2-yl)-coumarin) and L² (2-methylene-2H-chromene-3-(methyl carbonimidic)thioanhydride). The L¹ ligand was prepared by treating w-bromo-3-acetylcoumarin with 1,2-phenylenediamine whereas the ligand L² was prepared through substitution reaction ofw-bromo-3-acetylcoumarin with potassium thiocyanate in ethanol medium. The confirmation of the structures for L¹ and L² were done by (C.H.N.S.) elemental analysis, FT-IR, NMR and mass spectra. The metal complexes of cobalt(II), nickel(II), copper(II) and cadmium(II), with L¹ and L², were prepared and isolated in the solid state then characterized by (C.H.N.M) elemental analysis, proton and carbon-13 NMR, FT-IR and mass spectra. Furthermore, the thermal analysis (TG-DSC) for some complexes assisted us in the elucidation of the suggested structures of complexes and confirmed their thermal stability. The results obtained from elemental analysis, magnetic susceptibility and thermal analysis confirmed that all metal complexes were formed in 2:1 molar ratio of ligand to metal with octahedral structures except cadmium(II) complexes which were in a tetrahedron geometry with 1:1 mole ratio. The complexes are found to be soluble in DMF and DMSO. The results obtained from TG-DSC analysis revealed that the metal complexes were thermally stable with point decomposition over 350 °C. The DFT/TDDFT calculations were carried out to provide the electronic structures and spectra of the compounds.

Keywords

transition metal complexes of pyrazine ligands; theoretical studies of metal complexes

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References

[1] Abdel-Shafi, A.A., Khalil, M.M.H., Abdalla, H.H., and Ramadan, R.M., 2002, Ruthenium, osmium and rhodium-2,3-bis(2′-pyridyl)quinoxaline complexes, Transition Met. Chem., 27 (1), 69–74.

[2] AL-Hashime, S.M., Sarhan, B.M., and Alazawi, S.A.S., 2007, Synthesis and studies of some mixed-ligand metal complexes containing benzotriazole with some other ligands, J. Al-Nahrain Univ., 10 (2), 82–88.

[3] Al-Jibouri, M.N., 2014, Templatesynthesis, characterization and antimicrobial study of new metal complexes from 2,6-diaminopyridine and 1,4-dihydroquinoxalin-2,3-dione, Eur. Chem. Bull., 3 (4), 384–389.

[4] Appendino, G., Mercalli, E., Fuzzati, N., Arnoldi, L., Stavri, M., Gibbons, S., Ballero, M., and Maxia, A., 2004, Antimycobacterial coumarins from the Sardinian giant fennel (Ferulacommunis), J. Nat. Prod., 67 (12), 2108–2110.

[5] Badawy, M.A., Mohamed, G.G., Omar, M.M., Nassar, M.M., and Kamel, A.B., 2010, Synthesis, spectroscopic and thermal characterization of quinoxaline metal complexes, Eur. J. Chem., 1 (4), 282–288.

[6] Bejaoui, L., Rohlicek, J., and Hassen, R.B., 2018, New cobalt(II) complexes of ‘3-acetyl-4-hydroxy-2H-chromene-2-one’: Crystal structure and Hirshfeld surface analysis, fluorescence behaviour and antioxidant activity, J. Mol. Struct., 1173, 574–582.

[7] Cotton, F.A., Wilkinson, G., Murillo, C.A., and Bochmann, M., 1999, Advanced Inorganic Chemistry, 6^th Ed., John Wiley & Sons, Inc., New York, USA.

[8] Creaven, B.S., Egan, D.A., Kavanagh, K., McCann, M., Noble, A., Thati, B., and Walsh, M., 2006, Synthesis, characterization and antimicrobial activity of a series of substituted coumarin-3-carboxylatosilver(I) complexes, Inorg. Chim. Acta, 359 (12), 3976–3984.

[9] Devienne, K.F., Raddi, M., Coelho, R.G., and Vilegas, W., 2005, Structure–antimicrobial activity of some natural isocoumarins and their analogues, Phytomedicine, 12 (5), 378–381.

[10] Emmanuel‐Giota, A.A., Fylaktakidou, K.C., Litinas, K.E., Nicolaides, D.N., and Hadjipavlou‐Litina, D.J., 2001, Synthesis and biological evaluation of several 3‐(coumarin‐4‐yl)tetrahydroisoxazole and 3‐(coumarin‐4‐yl)dihydropyrazole derivatives, J. Heterocycl. Chem., 38 (3), 717–722.

[11] Grazul, M., and Budzisz, E., 2009, Biological activity of metal ions complexes of chromones, coumarins and flavones, Coord. Chem. Rev., 253 (21-22), 2588–2598.

[12] Geary, W.J., 1971, The use of conductivity measurements in organic solvents for the characterisation of coordination compounds, Coord. Chem. Rev., 7 (1), 81–122.

[13] Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, Jr., J.A., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., and Fox, D.J., 2009, Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford CT.

[14] Lee, C., Yang, W., and Parr, R.G., 1988, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B: Condens. Matter, 37, 785–789.

[15] Tomasi, J., Mennucci, B., and Cammi, R., 2005, Quantum mechanical continuum solvation models, Chem. Rev., 105 (8), 2999–3094.

[16] Brown D.J., Ellman J.A., and Taylor, E.C., 2004, Quinoxalines, Supplement 2-Chemistry of Heterocyclic Compounds: A Series of Monographs, 1^st Ed., Wiley-Interscience, New York.

[17] Kostova, I., Bhatia, S., Grigorov, P., Balkansky, S., Parmar, V.S., Prasad, A.K., and Saso, L., 2011, Coumarins as antioxidants, Curr. Med. Chem., 18 (25), 3929–3951.

[18] Kulkarni, N.V., Kurdekar, G.S., Budagumpi, S., and Revankar, V.K., 2010, Spectroscopy, structure, and electrochemistry of transition metal complexes having [M₂N₂OS₂] coordination sphere, J. Coord. Chem., 63 (18), 3301–3312.

[19] Liu, F., Martin-Mingot, A., Lecornué, F., Jouannetaud, M.P., Maresca, A., Thibaudeau, S., and Supuran, C.T., 2012, Carbonic anhydrases inhibitory effects of new benzenesulfonamides synthesized by using superacid chemistry, J. Enzyme Inhib. Med. Chem., 27 (6), 886–891.

[20] Cotton, F.A., Wilkinson, G., Murillo, C.A., and Bochmann, M., 1999, Advanced Inorganic Chemistry, 6^th Ed., John Wiley & Sons, Inc., New York.

[21] Morse, G.E., Paton, A.S., Lough, A., and Bender, T.P., 2010, Chloro boron subphthalocyanine and its derivatives: dyes, pigments or somewhere in between?, Dalton Trans., 39 (16), 3915–3922.

[22] Shaker, S.A., Khaledi, H., and Ali, H.M., 2011, Spectroscopic investigations and physico-chemical characterization of newly synthesized mixed-ligand complexes of 2-methylbenzimidazole with metal ions, Chem. Pap., 65 (3), 299–307.

[23] Silverstein, R.M., and Bassler, G.C., 1962, Spectrometric identification of organic compounds, J. Chem. Educ., 39 (11), 546.

[24] Wang, C.J., Hsieh, Y.J., Chu, C.Y., Lin, Y.L., and Tseng, T.H., 2002, Inhibition of cell cycle progression in human leukemia HL-60 cells by esculetin, Cancer Lett., 183 (2), 163–168.

[25] Wright, J.S., Johnson, E.R., and DiLabio, G.A., 2001, Predicting the activity of phenolic antioxidants: Theoretical method, analysis of substituent effects, and application to major families of antioxidants, J. Am. Chem. Soc., 123 (6), 1173–1183.

[26] Shaffer, C.J., Martens, J., Marek, A., Oomens, J., and Tureček, F., 2016, Photoleucine survives backbone cleavage by electron transfer dissociation. A near-UV photodissociation and infrared multiphoton dissociation action spectroscopy study, J. Am. Soc. Mass. Spectrom., 27 (7), 1176–1185.

[27] Manna, S., Mistri, S., Bhunia, A., Paul, A., Zangrando, E., and Manna, S.C., 2017, Manganese(IV) complex with a polydentate Schiff base ligand: Synthesis, crystal structure, TDDFT calculation, electronic absorption and EPR spectral study, J. Coord. Chem., 70 (2), 296–313.

DOI: https://doi.org/10.22146/ijc.43857