Studies on the vibrational frequencies and molecular electrostatic potential surfaces of the trans-bis-[O-3-methyl-1-butyl-(ferrocenyl)dithiophosphonato]nickel(II) complex

Öz

Vibrational spectroscopy (FT-IR and Raman) of trans-bis-[O-3-methyl-1-butyl-(ferrocenyl)dithiophosphonato]nickel(II) complex, [Ni(FcL)2], which was known previously has been reported. On the other hand, the density functional theory (DFT) calculations on the compound [Ni(FcL)2] have been performed to compare the experimental vibrational frequencies obtained from calculated vibrational frequencies of [Ni(FcL)2] complex for the first time. A relatively good correlation between experimental and theoretical frequencies were found for [Ni(FcL)2]. The molecular electrostatic potential (MEP) surface of the complex was also composed by DFT calculation using the optimized geometry at a B3LYP/LANL2DZ level.

Anahtar Kelimeler

• Ferrocenyl dithiophosphonato complexes
• density functional theory
• FT-IR
• vibrational frequencies
• molecular electrostatic potential

Trans-bis-[O-3-metil-1-bütil-(ferrosenil)ditiyofosfonato]nikel(II) kompleksinin titreşim frekansları ve moleküler elektrostatik potansiyel yüzeyleri üzerine çalışmalar

Öz

Trans- bis -[O-3- metil- 1- bütil- (ferrosenil) ditiyofosfonato]nikel(II) kompleksinin [Ni(FcL)2] titreşim spektroskopisi (FT-IR ve Raman) bildirildi. Öte yandan, [Ni(FcL)2] kompleksinin hesaplanan titreşim frekanslarından elde edilen deneysel titreşim frekanslarını ilk kez karşılaştırmak için [Ni(FcL)2] bileşiği üzerinde yoğunluk fonksiyonel teorisi (DFT) hesaplamaları yapılmıştır. [Ni(FcL)2] için deneysel ve teorik frekanslar arasında iyi bir korelasyon bulundu. Kompleksin moleküler elektrostatik potansiyeli (MEP) yüzeyi de B3LYP/LANL2DZ seviyesinde optimize edilmiş geometri kullanılarak DFT hesaplaması ile oluşturulmuştur.

Anahtar Kelimeler

• Ferrosenil ditiyofosfonato kompleksleri
• yoğunluk fonksiyonel teorisi
• FT-IR
• titreşim frekansları

Kaynakça

1. REFERENCES
2. [1] Walker, B.J., "Organophosphorus Chemistry", Penguin, London, (1972).
3. [2] Kosolapoff, G.M., "Organophosphorus Compounds", John Wiley&Sons, London, (1950).
4. [3] He, X.H., Tian, G.X., Chen, J., Rao, L.F., "Characterization of the extracted complexes of trivalent lanthanides with purified cyanex 301 in comparison with trivalent actinide complexes", Journal of the Chemical Society, Dalton Transactions, (2014), 43, 46, 17352-17357.
5. [4] Diemert, K., Kuchen, W., "Zur Kenntnis Der Organophosphorverbindungen, XVIII Dithiophosphinsäuren RR'P(S)SH, Ihre Synthese, Derivate und Metallkomplexe", Phosphorus, Sulfur and the Related Elements, (1977), 3, 2, 131-136.
6. [5] McCleverty, J.A., Kowalski, R.S.Z., Bailey, N.A., Mulvaney, R., O'Cleirigh, D.A., "Aspects of the inorganic chemistry of rubber vulcanisation. Part 4. Dialkyl- and diaryl-dithiophosphate and -dithiophosphinate complexes of zinc: phosphorus-31 nuclear magnetic resonance spectral studies and structures of [NMe4][Zn{S2P(OC6H4Me-p)2}3] and [NEt4][Zn(S2PPh2)3]", Journal of the Chemical Society, Dalton Transactions, (1983), 4, 627-634.
7. [6] Ageda, S., Fuke, C., Ihama, Y., Miyazaki, T., "The stability of organophosphorus insecticides in fresh blood", Legal Medicine, (2006), 8, 144-149.
8. [7] Kumar, S., Khajuria, R., Gupta, V.K., Kant, R., Pandey, S.K., "The first nickel(II) complexes of disubstituted diphenyldithiophosphates: Synthesis, spectroscopic, electrochemical, antifungal and single crystal X-ray analysis", Polyhedron, (2014), 72, 140-146.

9. [8] Kabra, V., Mitharwal, S., Singh, S., "Synthesis and Insecticidal Activity of Novel Dithiophosphonates", Phosphorus and Sulfur and the Related Elements, (2009), 184, 9, 2431-2442.
10. [9] Pasqualini, R B.E., Comazzi, V., Laine, J., "Radiopharmaceutical product having in particular a cerebral tropism comprising a nitruro complex of a transition metal and method for preparing said product", US5496929A, (1996).
11. [10] Lecher, H.Z., Greenwood, R.A., Whitehouse, K.C., Chao, T.H., "The Phosphonation of Aromatic Compounds with Phosphorus Pentasulfide", Journal of the American Chemical Society, (1956), 78, 19, 5018-5022.
12. [11] Thomsen, K.C., Scheibye, S., Lawesson, S.-O., "Thiation with 2,4-Bis(4-Methoxyphenyl)-1,3,2,4-Dithiadiphosphetane 2,4-Disulfide: N-methylthiopyrrolidone", Organic Syntheses, (1984), 62, 158.
13. [12] Karakus, M., Lonnecke, P., Hey-Hawkins, E., "Zwitterionic ferrocenyldithiophosphonates: the molecular structure of [FcP(S)S(OCH2CH2NH2Me)] [Fc = Fe(η5-C5H4)( η5-C5H5)]", Polyhedron, (2004), 23, 14, 2281-2284.
14. [13] Karakus, M., Lonnecke, P., Yakhvarov, D., Hey-Hawkins, E., "Heterobimetallic nickel(II) complexes of ferrocenyldithiophosphonates. Molecular structures of [{FcP(OR)S-2}(2)Ni] [Fc = Fe(η5-C5H4)( η5-C5H5), R = Et, Pr-i, Bu-s, Bu-i]", Zeitschrift für anorganische und allgemeine Chemie, (2004), 630, 10, 1444-1450.
15. [14] Van Zyl, W.E., "Dithiophosphonates and Related P/S-Type Ligands Of Group 11 Metals", Comments on Inorganic Chemistry, (2010), 31, 1-2, 13-45.
16. [15] Sánchez, G., Garcı́a, J.n., Meseguer.J., D., Serrano, J.L., Pérez, J., Molins, E.e., López, G., "Organometallic nickel(II) complexes with dithiophosphate, dithiophosphonate and monothiophosphonate ligands", Inorganica Chimica Acta, (2004), 357, 3, 677-683.
17. [16] Arca, M., Cornia, A., Devillanova, F.A., Fabretti, A.C., Isaia, F., Lippolis, V., Verani, G., "New perspectives in phosphonodithioate coordination chemistry. Synthesis and X-ray crystal structure of trans-bis-[O-ethyl-(4-methoxyphenyl)phosphonodithioato] nickel(II)", Inorganica Chimica Acta, (1997), 262, 1, 81-84.
18. [17] Gray, I.P., Milton, H.L., Slawin, A.M.Z., Woollins J.D., "Synthesis and structure of [Fc(RO)PS2]− complexes", Journal of the Chemical Society, Dalton Transactions, (2003), 17, 3450-3457.
19. [18] Sebastian, S., Sundaraganesan, N., Karthikeiyan, B., Srinivasan, V., "Quantum mechanical study of the structure and spectroscopic (FT-IR, FT-Raman, 13C, 1H and UV), first order hyperpolarizabilities, NBO and TD-DFT analysis of the 4-methyl-2-cyanobiphenyl", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, (2011), 78, 2, 590-600.
20. [19] Zeyrek, C.T., Alpaslan, G., Alyar H., Yildiz, M., Dilek, N., Unver, H., "Synthesis, molecular structure, spectroscopic and theoretical studies on E-2-ethoxy-4-[(4-ethoxyphenylimino)methyl]phenol", Journal of Molecular Structure, (2015), 1088, 14-27.
21. [20] Zeyrek, C.T., Dilek, N., Yildiz, M., Unver, H., "Synthesis, structure, spectroscopic (FT-IR) and density functional modelling studies of 1-[(4-ethoxyphenylimino)methyl]napthalene-2-ol", Molecular Physics, (2014), 112, 19, 2557-2574.
22. [21] Sağlam, E.G., Ebinç, A., Zeyrek, C.T., Ünver, H., Hökelek, T., "Structural studies on some dithiophosphonato complexes of Ni(II), Cd(II), Hg(II) and theoretical studies on a dithiophosphonato Ni(II) complex using density functional theory", Journal of Molecular Structure, (2015), 1099, 490-501.
23. [22] Saglam, E.G., Bulat, E., Zeyrek, C.T., Dal, H., Hokelek, T., "Syntheses of and structural studies on some square planar dithiophosphonato Ni(II) complexes, octahedral pyridine derivatives thereof and X-ray crystallography, DFT and molecular docking studies of the latter", Journal of Molecular Structure, (2019), 1178, 112-125.
24. [23] Sağlam, E.G., Akkoç, S., Zeyrek, C.T., Dal, H., Tutsak, Ö., "New heterobimetallic nickel(II) ferrocenyldithiophosphonato complexes: Syntheses, characterization, antiproliferative activity and X-ray, DFT, molecular docking studies on trans-bis-[O-3-methyl-1-butyl-(ferrocenyl)dithiophosphonato]nickel(II)", Inorganica Chimica Acta, (2021), 514, 119991.
25. [24] Frisch, G.W.T. M.J., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., et all. Gaussian 09, Gaussian, Inc.,, Wallingford, CT, (2009).
26. [25] Dennington, T.K. R., Millam J., in: S.M. KS. (Ed.) "GaussView, Semichem", Inc., (2009).
27. [26] Becke ,A.D., "Density‐functional thermochemistry. IV. A new dynamical correlation functional and implications for exact‐exchange mixing", The Journal of Chemical Physics, (1996), 104, 3,1040-1046.
28. [27] Lee, C., Yang W., Parr, R.G., "Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density", Physical Review B, (1988), 37, 2, 785-789.
29. [28] Perdew, J.P., Kurth, S., Zupan, A., Blaha, P., "Accurate Density Functional with Correct Formal Properties: A Step Beyond the Generalized Gradient Approximation", Physical Review Letters, (1999), 82, 12, 2544-2547.
30. [29] Sundaraganesan, N., Elango, G., Sebastian, S., Subramani ,P., "Molecular structure, vibrational spectroscopic studies and analysis of 2-fluoro-5-methylbenzonitrile", Indian Journal of Pure & Applied Physics, (2009), 47, 7, 481-490.
31. [30] Merrick, J.P., Moran, D., Radom, L., "An Evaluation of Harmonic Vibrational Frequency Scale Factors", The Journal of Physical Chemistry A, (2007), 111, 45, 11683-11700.
32. [31] Karakus, M., Yilmaz, H., Bulak, E., "Synthesis and Characterization of Zn(II) and Cd(II) Complexes with Bisdithiophosphonates", Russian Journal of Coordination Chemistry, (2005), 31, 5, 316-321.
33. [32] Gray, I.P., Slawin, A.M.Z., Woollins, J. Derek, "Synthesis and characterisation of disulfides and esters derived from their sodium organodithiophosphonate salts", New Journal of Chemistry, (2004), 28, 11,1383-1389.
34. [33] Aragoni, M.C., Arca M., Demartin, F., Devillanova, F.A., Graiff, C., Isaia, F., Lippolis, V., Tiripicchio, A., Verani, G., "Reactivity of phosphonodithioato NiII complexes: solution equilibria, solid state studies and theoretical calculations on the adduct formation with some pyridine derivatives", Journal of the Chemical Society, Dalton Transactions, (2001), 18, 2671-2677.
35. [34] Masahide, N., Yoshinori, K., Hisashi, K., "Studies of Bivalent Metal Chelates of 2-Aminomethylpyridine", Bulletin of the Chemical Society of Japan (1975), 48, 1, 245-249.
36. [35] Sunder, S., Hanlan, L., Bernstein, H.J., "Resonance Raman spectra of metal complexes of substituted dithiophosphinic acids", Inorganic Chemistry, (1975), 14, 8, 2012-2013.
37. [36] Yu-Mei, Z., Hong-Li, Z., "Synthesis and Crystal Structure of Novel Ferrocenyl Pyrrolidines through Multicomponent Reaction, Synthesis and Reactivity in Inorganic", Metal-Organic, and Nano-Metal Chemistry, (2014), 44, 8, 1115-1118.
38. [37] Politzer, D.G.T. P., "Plenum", New York, (1981).
39. [38] Politzer, P.a.M., J.S., "Protein", Adenine Press (1991).