Hasan NAZIR, Arda ATAKOL, EMİNE KÜBRA İNAL, NURCAN ACAR, Erdal EMİR, ORHAN ATAKOL

Synthesis, Thermal Kinetic Analysis and DFT Calculations of Pyrazine and Pyridine Complexes of Copper(II) Thiocyanate

Two NNN type ligands namely bis-2,6-(pyrazol-1-yl) pyridyne (pp) and bis-2,6-(3,5-dimethyl-pyrazol-1-yl) pyridyne (dmpp) were prepared by the use of 2,6-dichloropyridine, pyrazol and 3,5-dimethylpyrazol. Using these ligands with SCN co-ligand two mononuclear Cu(II) complexes were synthesized and characterized. The complexes were investigated by thermogravimetry (TG) and differential thermal analysis (DTA) and subjected to isothermal and nonisothermal kinetic analyses. TG and DTA results indicated that the complexes showed two distinctive degradation steps and the NNN type ligand was removed from the structure at temperatures above 300 °C. The activation energies of these complexes and same thermodynamic parameters of these thermal reactions have been calculated. The situation of d orbitals of Cu(II) ion, the electron densities of donor atoms of the ligands, natural bond orbital (NBO) analysis, the theoretical IR spectra and HOMO-LUMO energy levels computed by the use of DFT/B3LYP methods with 6-311G (d) basis set in Gaussian 09 software. These data were employed to enlighten the thermal degradation of the complexes prepared.

Anahtar Kelimeler:

Thermal kinetic analysis, KAS; OFW; Energetic materials

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[1] Jameson, D. L., Goldsby, K. A. 2,6-bis(N-pyrazolyl) pyridines. J. Org. Chem., 55 (1990), 4992-4994.
[2] Palion-Gazda, J., Machura, B., Kruszynski, R., Grancha, T., Moliner, N., Lloret, F., Julve, M. Spin Crossover in Double Salts Containing Six- and Four-Coordinate Cobalt(II) Ions. Inorg. Chem., 56 (2017), 6281-96.
[3] Kruger, C., Augustin, P., Nemec, I., Travnicek, Z., Oshio, H., Boca, R., Renz, F. Spin Crossover in Iron(III) Complexes with Pentadentate Schiff Base Ligands and Pseudohalido Coligands. Eur. J. Inorg. Chem., (2013),905-12.
[4] Broring, M., Kohler, S., Pietzonka, C. Pseudohalogenido complexes of iron-2,2'-bidipyrrins. J. Porphyrine and Phatalocyanines, 16 (2012), 641-50.
[5] Nijhuma, M., Samiran, M., Volker, G., S. Ozra, G., Abdul Malik, K. M. Synthesis, characterization and crystal structures of some four coordinated nickel(II) complexes with tridentate Schiff base ligands. Polyhedron, 20 (2001), 135-41.
[6] Kurtaran, R., Odabaşıoğlu, S., Azizoğlu, A., Kara, H., Atakol, O. Experimental and computational study on [2,6-bis(3,5-dimethyl-N-pyrazolyl) pyridine]-(dithiocyanato)mercury(II). Polyhedron, 26 (2007), 5069-5074.
[7] Arıcı, C., Ülkü, D., Kurtaran, R., Ergun, Ü., Atakol, O. Crystal Structure Analysis of [bis-2,6-(3,5-dimethylpyrazolyl)pyridine-dicyanato] copper(II) monohydrate. Crystal Res. Technol., 41 (2006), 309-313.
[8] Manikandan, P., Thomas, K. R. J., Manoharan, P. T. Structural and spectral diversities in copper(II) complexes of 2,6-bis(3,5-dimethyl- pyrazol-1-ylmethyl)pyridine]. J. Chem. Soc. Dalton Trans., (2000), 2779-83.
[9] Taştekin, M., Arıcı, C., Svoboda, I., Emregül, K. C., Kurtaran, R., Atakol O., Fuess, H. The Synthesis, structure and thermal decomposition of some Cu(II) complexes with NNN type ligands and thiocyanate anion. Z. Kristallogr., 222 (2007), 255-258.
[10] Grove, H., Julve, M., Lloret, F., Kruger, P.E., Tornroos, K. W., Sletten, J. Syntheses, crystal structures and magnetic properties of copper(II) polynuclear and dinuclear compounds with 2,3-bis(2-pyridyl)pyrazine (dpp) and pseudohalide as ligands. Inorg. Chim. Acta., 325 (2001), 115-124.
[11] Das, A., Bhattacharya, K., Giri, S., Ghosh, A. Synthesis, crystal structure and magnetic properties of a dinuclear and a trinuclear Ni(II) complexes derived from tetradentate ONNO donor Mannich base ligands. Polyhedron, 134 (2017), 295-301.
[12] Bhargavi, G., Rajasekharan, M. V., Costes, J. P. Synthesis, Crystal Structure and Magnetic Properties of [Mn((1R,2R)-Salcy)N-3/NCS] Complexes: Solvent Dependent Crystallization of Monomers, Chains and Dimers. Chem. Select., 2 (2017), 7975-82.
[13] Sarkar, M., Clerac, R., Mathoniere, C., Hearns, N. G. R., Bertolasi, V., Ray, D. Azido, Cyanato, and Thiocyanato Coordination Induced Distortions in Pentacoordinated [Co(II)A(bip)] (2) (A = NCS-, N-3(-), or NCO-) Complexes. Eur. J. Inorg. Chem., 31 (2009), 4675-4685.
[14] Talukder, P., Datta, A., Mitra, S., Rosair, G., El Fallah, M. S., Ribas, J. End-to-end single cyanato and thiocyanato bridged Cu(II) polymers with a new tridentate Schiff base ligand: Crystal structure and magnetic properties. Dalton Trans., (2004), 4161-67.
[15] Ercan, F., Atakol, O. Crystal structure of a new trinuclear copper(II) complex: C3L2(SCN)2.2.5 (C4H8O2), Z.Kristallogr., 221 (2006), 735-39.
[16] Ercan, F., Arıcı, C., Ülkü, D., Kurtaran, R., Aksu, M., Atakol, O. Synthesis and Crystal structure of two dimeric Cadmium Complexes bonded with pseudohalides,1.1 and 1.3 bonding. Z. Kristallogr., 219 (2014), 295-99.
[17] Grove, H., Julve, M., Lloret, F., Kruger, P. E., Tornroos, K. W., Sletten, J. Syntheses, crystal structures and magnetic properties of copper(II) polynuclear and dinuclear compounds with 2,3-bis(2-pyridyl)pyrazine (dpp) and pseudohalide as ligands. Inorg. Chim. Acta., 325 (2001), 113-24.
[18] Diaz, C., Ribas, J., Sanz, N., Solans, X., Font-Bardia, M. Synthesis,Crystal stryucture and Magnetic Properties of catena-poly[(2,2’-bipyridylcopper)-di-mü-thiocyanato] and bis (2,2’-bipyridyl)thiocyanatocopper(II) perchlo- rate. Inorg. Chim. Acta., 286 (199),169-74.
[19] Hazari, A., Giri, S., Diaz, C., Ghosh, A. Unusual site electron of NCS- in trinuclear complexes of Cu(II) and Ni(II) with a reduced N2O2 donor Schiff base. Polyhedron, 118 (2016), 70-80.
[20] Cortes, R., Luiz de Larramendi, J. I., Lezama, L., Rojo, T., Urtiaga, K., Arriortua, M. I. Synthesis, Structural ,Spectroscopic and Magnetic Studies Twoo Azido and Thiocyanato Nickel(II) Dinuclear Complexes with Ferromagnetic Interactions, J. C. S. Dalton Trans., (1993), 2723-28.
[21] Charlot, M. F., Kahn, O., Chaillet, M., Larrieu, C. Interaction between Copper(II) Ions through the Azido Bridge Concept of Spin Polarization and Abinitio Calculations on Model Systems. J. Am. Chem. Soc., 103 (1986), 2754-81.
[22] Cabort, A., Therrien, B., Bernauer, K., Süss-Fink, G. Copper(II) Azido complexes containing trinitrogen ligands. Inorg. Chim. Acta., 349 (2003), 78-84.
[23] Deoghoria, S., Sain, S., Soler, M., Wong, W. T., Christou, G., Bera, S. K., Chandra, S. K. Synthesis, Crystal Structure and Magnetic Properties of a new Ferromagnetic nickel(II) dimer derived from a hexadentate Schiff Base Ligand. Polyhedron., 22 (2003), 257-62.
[24] Coats, A. W., Redfern, J. P. Kinetic parameters from thermogravimetrical data. Nature, 201 (1964), 68-9.
[25] Ebrahimi, H. P., Hadi, J. S., Abdulnabi, Z. A., Bolandnazar, Z. Spectroscopic, thermal analysis and DFT computational studies of salen-type Schiff base complexes. Spectrochim. Acta Part A, 117 (2014), 485-492.
[26] Ozawa, T. Kinetic Analysis of derivative curves in thermal analysis. J. Therm. Anal., 2 (1970), 301-324.
[27] Koga, N. Ozawa’s kinetic method for analysing thermoanalytical curves. J. Therm. Anal. Cal., 113 (2013), 1527-1541.
[28] Kissenger, H. E. Reaction Kinetics in Differential Thermal Analysis. Anal.Chem., 29(1957),1702-6.
[29] Frisch, M. J., Trucks, G.W., et al. Gaussian 09, Revision D.01. Gaussian Inc. Wallingford CT. 2009.
[30] Sarada, K., Muraleedharan, K. Effect of addition of silver on the thermal decomposition kinetics of copper oxalate. J. Therm. Anal. Cal., 123 (2016), 643-51.
[31] Çılgı, G. K., Çetişli, H.,Donat, R. Thermal Kinetic analysis of Uranium Salts. J. Therm. Anal. Cal., 115 (2014), 2007-20.
[32] Kullyyakool, S., Danvirutai, C., Siriwong, K., Noisong, P. Determination of kinetic triplet of the synthesized Ni3(PO4)2.8H2O by non-isothermal and isothermal kinetic methods. J. Therm. Anal. Cal., 115 (2014), 1497-507.
[33] Abdel-Kader, N. S., Amin, R. M., El-Ansary, A. L. Complexes of Schiff base of benzopyran-4-one derivative. J. Therm. Anal. Cal., 123 (2016), 1695-1706.
[34] Wu, B. D., Bi, Y. G., Zhou, M. R., Zhang, T. L, Yang, L., Zhou, Z. N., Zhang, J. G. Stable High Nitrogen Energetic Trinuclear Compounds Based on 4-Amino-3,5-dimethyl-1,2,4-Triazole. Z. Anorg. Allg. Chem., 640 (2014), 1467-73.
[35] Ergun, Ü., Atakol, O., Eriş, F. Z., Yücel, ., Düzgün, E. Estimation of Coordination Bond Energies of NH3, H2O and Et2NH Ligands in the Ni(II) and Cu(II) complexes. J. Therm. Anal. Cal., 97 (2009), 1007-1014.
[36] Addison, A. W., Nageswara Rao, T., Reedijk, J., Van Rijn, J., Verschoor, G. C. Synthesis, Structure and Spectroscopic Properties of Copper(II) Compounds containing Nitrogen-Sulphur Donor Ligands. J. C. S. Dalton Trans., (2001), 3149-3156.