SPECTROSCOPIC STUDY OF COMPLEX FORMATION OF COPPER(II) WITH (S)-β-[3-ISOBUTYL-4-(2-METALLYL)-5-THIOXO-1,2,4-TRIAZOL-1-YL]-α-ALANINE IN AQUEOUS SOLUTION
Abstract
The complex formation of (S)-β-[3-isobutyl-4-(2-methallyl)-5-thioxo-1,2,4-triazol-1-yl]-α-alanine amino acid with copper(II) chloride in aqueous solution has been investigated by means of UV-Vis and IR spectroscopy at 25 °C. The molar ratio method was used to determine the composition of that complex. It has been established that a complex compound of the ML2 type is formed in aqueous solution. Based on the data of UV-Vis spectra, the stability constant of this complex was calculated. The stability constant of the ML2 type complex is equal to (4.23±0.27)·106 L2·mol-2. In addition, on the basis of IR spectroscopy data the formation of the complex was confirmed, and the centers of the ligand involved in the complex formation were identified. In the IR spectrum of the complex isolated from the solution and dried in air, a new weak absorption band appears, which is characteristic of the coordination of the copper(II) ion with the carboxylate ion. In addition, there is a shift of the stretching vibration band of the N-H amino group to the region of large values, which indicates the participation of the lone electron pair of the nitrogen of the amino group in the formation of coordination with the copper(II) ion. Moreover, an absorption band of coordination water in the structure of the complex is also observed. Based on the data obtained, the structure of the chelate complex has been proposed, in which the copper(II) cation is bound to the oxygen atom of the carboxylate anion by electrostatic interaction, and to the nitrogen atom of the amino group by a covalent bond by the donor-acceptor mechanism. And the octahedral coordination sphere of the copper(II) ion is complemented by two water molecules.
For citation:
Sargsyan H.R., Grigoryan G.S., Markarian Sh.A. Spectroscopic study of complex formation of copper(II) with (S)-β-[3-isobutyl-4-(2-metallyl)-5-thioxo-1,2,4-triazol-1-yl]-α-alanine in aqueous solution. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 2. P. 62-69. DOI: 10.6060/ivkkt.20236602.6740.
References
Sadovnikova M.S., Belikov V.M. Industrial Applications of Aminoacids. Russ. Chem. Rev. 1978. V. 47. N 2. P. 199-212. DOI: 10.1070/RC1978v047n02ABEH002212.
Abendrot M., Chęcińska L., Kusz J., Lisowska K., Zawadzka K., Felczak, A.,Kalinowska-Lis U. Zinc(II) Complexes with Amino Acids for Potential Use in Dermatology: Synthesis, Crystal Structures, and Antibacterial Ac-tivity. Molecules. 2020. V. 25. N 4. P. 951. DOI: 10.3390/molecules25040951.
Stănilă A., Braicu C., Stănilă S., Pop R.M. Antibacterial Activity of Copper and Cobalt Amino Acids Complexes. Not. Bot. Horti Agrobo. 2011. V. 39. N 2. P. 124. DOI: 10.15835/nbha3926847.
Zayed M.E., Ammar R.A. Some transition metal ions complexes of tricine (Tn) and amino acids: pH-titration, synthesis and antimicrobial activity. J. Saudi Chem. Soc. 2014 V. 18. N 6, P. 774-782. DOI: 10.1016/j.jscs.2011.08.006.
Stanila A., Marcu D., Rusu. D., Rusu M, David L. Spectroscopic studies of some copper(II) complexes with amino acids. J. Mol. Struct. 2007. V. 834–836. P. 364. DOI: 10.1016/j.molstruc.2006.11.048.
Bukharov M.S., Shtyrlin V.G., Mukhtarov A.S., Mamin G.V. Study of structural and dynamic characteristics of copper(II) amino acid complexes in solutions by combined EPR and NMR relaxation methods. Phys. Chem. Chem. Phys. 2014. V. 16. P. 9411. DOI: 10.1039/c4cp00255e.
Izumi Y., Chibata I., Itoh T. Production and Utilization of Amino Acids. Angew. Chem. Int. Ed. Engl. 1978. V. 17. N 3. P. 176. DOI: 10.1002/anie.197801761.
Saghyan A.S., Mkrtchyan A.F., Simonyan H.M, Hovhannisyan N.A., Hovhannisyan A.M., Langer P., Belokon Yu.N. New Generations of Optically Active Non-Proteinogenic α-Amino Acids, Synthesis and Study. Chem. J. Armenia. 2016. V. 69. N 1-2. P. 81.
Singh S., Rao S.J., Pennington M.W. Efficient Asymmetric Synthesis of (S)- and (R)-N-Fmoc-S-Trityl-α-methylcysteine Using Camphorsultam as a Chiral Auxiliary. J. Org. Chem. 2004. V. 69. N 13. P. 4551. DOI: 10.1021/jo049622j.
DeAlba-Montero I., Guajardo-Pacheco J., Morales-Sánchez E., Araujo-Martínez R., Loredo-Becerra G.M., Martínez-Castañón G.-A., Ruiz F., Compeán Jasso M.E. Antimicrobial Properties of Copper Nanoparticles and Ami-no Acid Chelated Copper Nanoparticles Produced by Using a Soya Extract. Bioinorg. Chem. Appl. 2017. P. 1–6. DOI: 10.1155/2017/1064918.
El-Saghier A. M., Abd El-Halim H. F., Abdel-Rahman, L. H., Kadry A. Green Synthesis of new Trizole Based Het-erocyclic Amino Acids Ligands and their Transition Metal Complexes. Characterization, Kinetics, Antimicrobial and Docking Studies. Appl. Organomet. Chem. 2018. P. e4641. DOI: 10.1002/aoc.4641.
Refat M.S., El-Sayed M.Y., Adam A.M.A. Cu(II), Co(II) and Ni(II) complexes of new Schiff base ligand: Synthesis, thermal and spectroscopic characterizations. J. Mol. Struct. 2013. V. 1038. P. 62–72. DOI: 10.1016/j.molstruc.2013.01.059.
Mohamad A.D.M., El-Shrkawy E.R., Al-Hussein M.F.I., Adam M.S.S. Water-soluble Cu(II)-complexes of Schiff base amino acid derivatives as biological reagents and sufficient catalysts for oxidation reactions. J. Taiwan Inst. Chem. Eng. 2020. V. 113. P. 27-45. DOI: 10.1016/j.jtice.2020.08.010.
Dadayan S.A., Dadayan A.S., Poghosyan A.S., Saghyan А.S., Grigoryan N.Y., Mangasaryan S.H., Khrustalev V.N., Maleev V.I., Langer P. A Novel Bromine- Containing Chiral Auxiliaries and NiII Complexes of their Schiff's Bases with Glycine and Alanine. Chem. J. Armenia. 2012. V. 65. N 3. P. 307-316 (in Russian).
Saghyan A.S., Simonyan H.M., Petrosyan S.G., Hakobyan K.V., Khachatryan L.V., Geolchanyan A.V., Ghochikyan T.V, Harutyunyan V.S. Asymmetric synthesis of new substituted 1,2,4-triazole containing analogs of (S)-α-alanine. Chem. J. Armenia. 2011. V. 64. N 3. P. 352-360 (in Russian).
Bychkova S.A., Gorboletova G.G., Frolova K.O. Study of Complex Formation of Co (II) with Triglycine in Aqueous Solution. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2020. V. 63. N 2. P. 21-25 (in Rus-sian). DOI: 10.6060/ivkkt.20206302.6020.
Safarmamadov S.M., Mirzokhonov D.Ch., Mabatkadamzoda K.S. Complex Formation of Cadmium (II) with 2-Methylimidazole in Aqueous and Aqueos-Alcohol Solutions. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2020. V. 63. N 10. P. 36-45 (in Russian). DOI: 10.6060/ivkkt.20206310.6201.
Sargsian H.R., Belluyan M.V., Markarian Sh.A. UV-vis Spectrophotometric Study of Copper (II) Chloride and Nitrate Complexes in Diethylsulfoxide. Uch. Zapiski EGU. 2007. N 1. P. 51-56 (in Russian).
Маrkarian S.A., Ghazoyan H.H., Sargsyan H.R., Shaninyan G.A. Thermodynamic and Spectroscopic (UV–Vis, FT IR) Studies of Solutions of CoCl2 (or NiCl2) in Diethylsulfoxide. J. Solution Chem. 2019. V. 48. N 10. P. 1378-1392. DOI: 10.1007/s10953-019-00924-9.
Bulatov M.I., Kalinkin I.P. A practical guide to photomet-ric methods of analysis. L.: Khimiya. 1986. 430 p. (in Russian).
Sverdlova O.V. Electronic spectra in organic chemistry. L.: Khimiya. 1985. 204 p. (in Russian).
Zheleznova T.Y., Vlasova I.V., Dobrovol’skiy S.M., Filatova D.V. Spectrophotometric Determination of Constants of Stability of Complex Compounds Using Algorithm of Mul-tiple Linear Regression. Analitika Kontrol. 2012. V. 16. N. 4. P. 350-357 (in Russian).
Kochergina L.A., Ratkova E.L. Thermodynamic Characteristics of Cu2+ Complexation Processes with L-phenylalanine in an Aqueous Solution. Russ. J. Coord. Chem. 2008. V. 34. N 8. P. 612–618. DOI: 10.1134/S1070328408080095.
Kuznetsova N.S. Synthesis, Investigation of the Structure and Properties of Complex Compounds of Hydroxyl Amino Acids with Copper Ions. IRJ. 2021. V. 114. N 12. P. 180-183. DOI: 10.23670/IRJ.2021.114.12.030.
Silverstein R.M., Webster F.X., Kiemle D.J. Spectrometric Identification of Organic Compounds. N.-Y.: John Wiley & Sons. 2005. 550 p.
Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds. H: John Wiley & Sons. 1986. 432 p.
