Theoretical Investigations on Vic-Dioxime Complexes Coordinated with Cu(II) and Ni(II) Ions: Using Density Functional Theory

Abstract

Metal complexes containing vic-dioximes are currently of interest due to their diverse properties and potential applications in various chemical processes, including medicine, where they serve as well-known antimicrobial agents, biology, catalysis, electrochemical sensors, and metallurgy. A vicinal dioxime ligand coordinated with CuII and NiII ions complexes were studied by using Density Functional Theory methods by using Gaussian 09. The optimized ground state structures of the complexes were calculated with mPW1PW91 iop(3/76=0572004280) method. Different basis sets have been selected for each atom as follows: Sulphur: cc-pVQZ, Carbon and Hydrogen: 6-31+G(d,p), Nitrogen: 6-31+G(2d), Oxygen: cc-pVQZ and Metal: Copper/Nickel: SDDALL, SDD. The both complexes have achieved fully optimized ground state geometries characterized by square planar structures surrounding the central metal atoms. Based on the molecular orbital descriptor values, the hardness is determined to be 1.60 eV for [Cu(II)L2] and 1.47 eV for [Ni(II)L2] complexes, respectively. Both complexes show considerable potential for use in nonlinear optics applications.

Keywords

• Vicinal dioxime Cu (II) and Ni (II) complexes
• Molecular orbital descriptors
• Infrared Spectra
• DFT

References

1. [1] Milios, C. J., Stamatatos, T. C., and Perlepes, S. P., "The Coordination Chemistry of Pyridyl Oximes", Polyhedron, 25: 134–194, (2006).
2. [2] Smith, A. G., Tasker, P. A., and White, D. J., "The Structures of Phenolic Oximes and Their Complexes", Coordination Chemistry Reviews, 241: 61–85, (2003).
3. [3] Stynes, D. V, Vernik, I., and Zobi, F., "Iron Complexes of Borylated Vicinal Dioxime Macrocycles", Coordination Chemistry Reviews, 233: 273–287, (2002).
4. [4] Kukushkin, V. Y. and Pombeiro, A. J. L., "Additions to Metal-Activated Organonitriles", Chemical Reviews, 102: 1771–1802, (2002).
5. [5] Kukushkin, V. Y., Tudela, D., and Pombeiro, A. J. L., "Metal-Ion Assisted Reactions of Oximes and Reactivity of Oxime-Containing Metal Complexes", Coordination Chemistry Reviews, 156: 333–362, (1996).
6. [6] Chakravorty, A., "Electroprotic Phenomena and Metal Oxidation States", Comments on Inorganic Chemistry, 4: 1–16, (1985).
7. [7] Egneus, B., "Investigations of Dioximes and Their Metal Complexes: A Survey of the Literature since 1963", Talanta, 19: 1387–1419, (1972).
8. [8] Bresciani-Pahor, N., Forcolin, M., Marzilli, L. G., Randaccio, L., Summers, M.F., and Toscano, P.J., "Organocobalt B12 Models: Axial Ligand Effects on the Structural and Coordination Chemistry of Cobaloximes", Coordination Chemistry Reviews, 63: 1–125, (1985).

9. [9] Pahor, N. B., Dreos, R., Geremia, S., Randaccio, L., Tauzher, G., and Zangrando, E., "Syntheses, Rate Constants, and X-Ray Structures of Alkylrhodoximes with Sigma-Donating Alkyl-Groups Me, Et, and i-Pr. A Comparison with the Analogous Alkylcobaloximes, a Vitamin-B12 Model", Inorganic Chemistry, 29: 3437–3441, (1990).
10. [10] Chakravorty, A., "Structural Chemistry of Transition Metal Complexes of Oximes", Coordination Chemistry Reviews, 13: 1–46, (1974).
11. [11] Thomas, T. W. and Underhill, A. E., "Metal–Metal Interactions in Transition-Metal Complexes Containing Infinite Chains of Metal Atoms", Chemical Society Reviews, 1: 99–120, (1972).
12. [12] Gok, Y. and Kantekin, H., "Synthesis and Characterization of Novel (E, E)-Dioxime and Its Mono-and Heterotrinuclear Complexes", Acta Chemica Scandinavica, 51: 664-671, (1997). DOI: 10.3891/acta.chem.scand.51-0664
13. [13] Kuse, S., Motomizu, S., and Tôei, K., "O-Diketonedioxime Compounds as Analytical Reagents for the Spectrophotometric Determination of Nickel", Analytica Chimica Acta, 70: 65–76, (1974).
14. [14] Çalişkan, Ş. G., "DFT, Molecular Docking, Bioactivity and ADME Analyses of Vic-Dioxim Ligand Containing Hydrazone Group and Its Zn (II) Complex", Current Computer-Aided Drug Design, 20: 264–273, (2024).
15. [15] Çalişkan, Ş. G., Genç, O., Erol, F., and Sarikavakli, N., "Molecular Docking, HOMO-LUMO, Quantum Chemical Computation and Bioactivity Analysis of Vic-Dioxim Derivatives Bearing Hydrazone Group Ligand and Their NiII and CuII Complexes", Gazi University Journal of Science Part A: Engineering and Innovation, 9: 299–313, (2022).
16. [16] Frisch, M. J., et al. "Gaussian 16, Rev. C.01", Gaussian 16, Rev. C. 01, (2016).
17. [17] Adamo, C. and Barone, V., "Exchange Functionals with Improved Long-Range Behavior and Adiabatic Connection Methods without Adjustable Parameters: The m PW and m PW1PW Models", The Journal of Chemical Physics, 108: 664–675, (1998).
18. [18] Legault, C. Y., "CYLview, 1.0b", Université de Sherbrooke, (2009).
19. [19] Dennington, R., Keith, T. A.., and Millam, J. M., "GaussView 6", Gaussian, (2016).
20. [20] O’boyle, N. M., Tenderholt, A. L., and Langner K. M., "Cclib: A Library for Package-Independent Computational Chemistry Algorithms", Journal of Computational Chemistry, 29: 839–845, (2008).
21. [21] Politzer, P., Laurence, P. R., and Jayasuriya K., "Molecular Electrostatic Potentials: An Effective Tool for the Elucidation of Biochemical Phenomena", Environmental Health Perspectives, 61: 191–202, (1985).
22. [22] Politzer, P. and Murray, J. S., "The Fundamental Nature and Role of the Electrostatic Potential in Atoms and Molecules", Theoretical Chemistry Accounts, 108: 134–142, (2002).
23. [23] Politzer, P. and Truhlar, D. G., “Chemical applications of atomic and molecular electrostatic potentials: reactivity, structure, scattering, and energetics of organic, inorganic, and biological systems”, Springer Science & Business Media, (2013).
24. [24] Ahsen, V., Musluoǧlu, E., Gürek, A., Gül, A., Bekâroǧlu, Ö., and Zehnder, M., "Synthesis and Complexation of 1,2‐Bis[(Monoaza[15]Crown‐5)‐ N ‐yl]Glyoxime. Crystal Structure of (1,2‐Bis[(Monoaza[15]Crown‐5)‐ N ‐yl]Glyoximato)Palladium(II)", Helvetica Chimica Acta, 73: 174–179, (1990).
25. [25] Gul, A. and Bekaroglu, O., "The Synthesis and Complex Formation of 5,6-Dihydrocyclopent [F, G] Acenaphthylene-1,2-Dione Dioxime", Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 12: 889–897, (1982).
26. [26] Gül, A. and Bekâroǧlu, Ö., "Synthesis of N, N’-Bis (4’-Benzo [15-Crown-5])-Diaminoglyoxime and Its Complex with Cu (II), Ni (II), Co (II), Pt (II), Pd (II) and UO2 (VI)", Journal of the Chemical Society, Dalton Transactions, 2537: 2537–2541, (1983).
27. [27] Ertas, M., Ahsen, V., Gül, A., and Bekâroğlu, Ö., "Synthesis of a Novel [10]Ferrocenophanedioxime with Bridge Heteroatoms and of Its Nickel(II) Complex", Journal of Organometallic Chemistry, 335: 105–108, (1987).
28. [28] Canpolat, E. and Kaya, M., "Synthesis and Characterization of a Vic-Dioxime Derivative and Investigation of Its Complexes with Ni(II), Co(II), Cu(II) and UO2(VI) Metals", Journal of Coordination Chemistry, 55: 961–968, (2002).
29. [29] Ma, M.S. and Angelici, R.J., "Novel Transition-Metal Complexes of Camphorquinone Dioxime Ligands", Inorganic Chemistry, 19: 363–370, (1980).
30. [30] Nogheu, L. N., Ghogomu, J. N., Mama, D. B., Nkungli, N. K., Younang, E., and Gadre, S. R., "Structural, Spectral (IR and UV/Visible) and Thermodynamic Properties of Some 3d Transition Metal (II) Chloride Complexes of Glyoxime and Its Derivatives: A DFT and TD-DFT Study", Computational Chemistry, 4: 119, (2016).
31. [31] Zülfikaroğlu, A., "Quantum Chemical Computational Studies on a Vic-Dioxime Ligand and Its Nickel Complex", Anadolu University Journal of Science and Technology A-Applied Sciences and Engineering, 18: 640–653, (2017).
32. [32] Babahan, I., Özmen, A., and Aslan, K., "Synthesis and Use of Dioxime Ligands for Treatment of Leukemia and Colon Cancer Cells", Applied Organometallic Chemistry, 31: e3752, (2017).
33. [33] Coşkun, A., Yılmaz, F., and Akgemci, E. G., "Synthesis, Characterization and Electrochemical Investigation of a Novel Vic-Dioxime Ligand and Its Some Transition Metal Complexes", Journal of Inclusion Phenomena and Macrocyclic Chemistry, 60: 393–400, (2008).
34. [34] Irving, H. and Williams, Rjp., "637. The Stability of Transition-Metal Complexes", Journal of the Chemical Society (Resumed), 3192–3210, (1953).
35. [35] Ahsen, V., Musluoǧlu, E., Gürek, A., Gül, A., Bekâroǧlu, Ö., and Zehnder, M., "Synthesis and Complexation of 1, 2‐Bis [(Monoaza [15] Crown‐5)‐N‐yl] Glyoxime. Crystal Structure of (1, 2‐Bis [(Monoaza [15] Crown‐5)‐N‐yl] Glyoximato) Palladium (II)", Helvetica Chimica Acta, 73: 174–179, (1990).
36. [36] Li Y. J., Guo, S. Z., Feng, T., Xie, K. F., and Dong, W. K., "An Investigation into Three-Dimensional Octahedral Multi-Nuclear Ni (II)-Based Complexes Supported by a More Flexible Salamo-Type Ligand", Journal of Molecular Structure, 1228: 129796, (2021).
37. [37] Zhao, Y. and Truhlar, D. G., "The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Function", Theoretical Chemistry Accounts, 120: 215–241, (2008).
38. [38] Koopmans, T., "Über Die Zuordnung von Wellenfunktionen Und Eigenwerten Zu Den Einzelnen Elektronen Eines Atoms", Physica, 1: 104–113, (1934).
39. [39] Parr, R. G., Szentpály, L. V, and Liu, S., "Electrophilicity Index", Journal of the American Chemical Society, 121: 1922–1924, (1999).
40. [40] Sheela, N. R., Muthu, S., and Sampathkrishnan, S., "Molecular Orbital Studies (Hardness, Chemical Potential and Electrophilicity), Vibrational Investigation and Theoretical NBO Analysis of 4-4′-(1H-1, 2, 4-Triazol-1-Yl Methylene) Dibenzonitrile Based on Abinitio and DFT Methods", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 120: 237–251, (2014).
41. [41] Mandal, U., Beg, H., and Misra, A., "Effect of Charge Transfer on the First Hyper-Polarizability of N,N-Dimethylaniline and Julolidine: A DFT Based Comparative Study", Journal of Molecular Modeling, 29: 1–15, (2023).
42. [42] Socrates, G., “Infrared and Raman characteristic group frequencies: tables and charts”, John Wiley & Sons, (2004).
43. [43] Fleming, I. and Williams, D., “Spectroscopic Methods in Organic Chemistry”, Springer International Publishing, Cham, (2019).
44. [44] Nakamoto, K., Morimoto, Y., and Martell, A. E., "Infrared Spectra of Metal Chelate Compounds. IV. Infrared Spectra of Addition Compounds of Metallic Acetylacetonates1a", Journal of the American Chemical Society, 83: 4533–4536, (1961).
45. [45] Dolaz, M., Tümer, M., Gölcü, A., and Serin, S., "Synthesis and Spectrophotometric Investigation of a New Vic-Dioxime Ligand and Its Transition Metal Complexes", Turkish Journal of Chemistry, 25: 491–500, (2001).