Quantum-chemical analysis of formation reactions of Со<sup>2+</sup> complexes





cobalt(II), complexe, effective nuclear charge, stability constant, correlation


Based on the analysis of quantum chemical calculations results (GAMESS, density functional theory, B3LYP method) as to coordination compounds of Co2+ions with H2O, NH3, OH, F, Cl, Br, I, CN, Ac, Akgenerally given by
[Co(H2O)6–nLn]2+nx, it has been demonstrated that within the selected series of ligands, there is no correlation between the amount of energy of monosubstituted cobalt aqua complexes formation(∆Е) and pK1,just like between the effective nuclear charge of the central atom (z*Со) and pK1. According to the behavior of ∆Е and z*Со,we identified two groups of ligands. The first group (OH, F, Ac, Ak, CN, NH3) demonstrates logical ∆Е decrease caused by the growth of z*Со. On the contrary, the second group (Cl, Br, I) demonstrates ∆Е increase caused by the growth of z*Со. This phenomenon is explained by the change in electronegativity and polarizability of donor atoms in groups and periods of the periodic table. It is established that linear correlations given by lgK = A + B·z*Со can be actualized only for complexes having ligands with similar donor atoms. Referring to the literature on stepwise complex formation of hydroxide, amine and chloride cobalt complexes in combination with z*Со calculations results, we determined A and B constants of lgK, z*Со-correlations for the atoms of oxygen (30.2, –17.7); nitrogen (125.4, –69.9) and chlorine
(–6.3, 5.8). The existence of the detected correlation series enables us to lean on lgK,z*М–dependence parameters for the fixed donor atom and to determine Kn values for various complexes with complex-based ligands using calculations and z*М data. This applies to complexes having central atoms of the same nature as well as simple monodentate ligands. The mentioned approach was used to calculate the stability constants for acrylate cobalt complexes (lgK1 = 1.2 и lgК2 = 4.3), which are not covered in literature.

Author Biographies

Viktor F. Vargalyuk, Oles Honchar Dnipropetrovsk National University, 72 Gagarin Ave., Dnipro, 49010

химический факультет, декан

Andrey O. Borshchevich, Oles Honchar Dnipropetrovsk National University, 72 Gagarin Ave., Dnipro, 49010

химический факультет, аспирант

Larisa V. Borshchevich, Oles Honchar Dnipropetrovsk National University, 72 Gagarin Ave., Dnipro, 49010

кафедра физической и неорганической химии. доцент

Vladimir O. Seredyuk, Oles Honchar Dnipropetrovsk National University, 72 Gagarin Ave., Dnipro, 49010

НИЛ теоретических и прикладных проблем химии кафедры органической химии, старший научный сотрудник


Mayakova, М. N., Alekseev, V. G. (2016). Experimental and theoretical study of Zn(II) complexation with ceftriaxone. Russ. J. Inorg. Chem., 61(3), 314-316. doi: 10.7868/S0044457X1603017X CrossRef

Alekseev, V. G. (2016). Experimental study and computer modeling of Ni(II) and Cu(II) complexation with ceftazidime. Russ. J. Inorg. Chem., 61(4), 531-534. doi: 10.7868/S0044457X16040024 CrossRef

Korobeinikova, E. Y., Merkulov, D. А. (2015). Equilibrium of cobalt(II) and nickel(II) complex formation in aqueous solutions of nitrilotrimethylphosphonic and dicarboxylic acids. Chemical Physics and Mesoscopycs, 17(1), 121–125. (in Russian). Retrieved from https://elibrary.ru/download/elibrary_23265280_73260323.pdf e-library

Korobeinikova, E. Y., Merkulov, D. А. (2013). Exploring the processes of cobalt(II) and nickel(II) complex formation with nitrilotrimethylphosphonic acid. The Bulletin of Udmurt University. Physics, Chemistry, 4, 11-14. (in Russian). Retrieved from http://en.vestnik.udsu.ru/files/originsl_articles/vuu_13_044_02.pdf vestnik.udsu.ru

Gridchin, S. N., Nikol’skii, V. M., Tolkacheva, L. N. (2015). Stability constants of the complexes of ethylene-diamine-N,N′-diglutaric acid with zinc, cadmium, cobalt, and manganese(II) ions. Russ. J. Inorg. Chem., 60(3), 383–386. doi: 10.7868/S0044457X15030071 CrossRef

Proskurnin M. A., Kononets M. Yu., Chernysh V. V. (2004). Correlations of the stability constants of complexes determined by thermal lensing. Moscow University Chemistry Bulletin. 59(1), 35–41. (in Russian). Retrieved from http://chem.msu.ru/rus/vmgu/041/51.pdf chem.msu.ru

Karapetyanz, M. Ch. (2014). [Methods of comparative calculation of physico-chemical properties]. Moskow, Russian Federation: Lenand (in Russian).

Stetsyk, V. V. (2016). Correlations of general and stepwise constants of coordination compounds. Young Scientist, 4(31), 298–310. (in Ukrainian). Retrieved from http://molodyvcheny.in.ua/files/journal/2016/4/73.pdf molodyvcheny.in.ua

Scopenko, V. V. (1997). [Coordination Chemistry: Textbook]. Kiev, Ukraine: Lybid (in Ukrainian).

Rios-Reyes, С. H., Hilda, C., Mendoza-Huizar, L. H., Reyes-Cruz, V. E., Rodríguez, M.-A. V. (2013). Kinetical study about the cobalt electrodeposition onto polycrystalline platinum. Quim. Nova, 36(7), 978-983. doi: 10.1590/S0100-40422013000700010 CrossRef

Golgovici, F., Mares, M. L., Cojocaru, A. (2014). Electro-deposition of Cobalt and Cobalt-Antimony from Non-Aqueous Media Containing Ethylene Glycol. Rev. Chim., 65(1), 98-104. Retrieved from http://www.revistadechimie.ro/-pdf/GOLGOVICI%20F.pdf%201%2014.pdf revistadechimie.ro

Mendoza-Huizar, L. H., Robles, J., Palomar-Pardave, M. (2002). Nucleation and growth of cobalt onto different substrates Part I. Underpotential deposition onto a gold electrode. J. Electroanal. Chem., 521, 95–106. doi: 10.2478/s11532-013-0269-5 CrossRef

Liu, Y., Li, Z. J., Wang, Y. Ch., Wang, W. (2014). Electrochemical reduction process of Co(II) in citrate solution. Trans. Nonferrous Met. Soc. China. 24, 876−883. doi: 10.1016/S1003-6326(14)63138-1 CrossRef

Gapon, Y. K., Sahnenko, N. D., Ved, M. V., Nenasitina, T. A. (2014). The rules of cobalt complexes formation // The Bulletin of NTU «KhPI», 51(1093), 136–140. (in Russian). Retrieved from http://repository.kpi.kharkov.ua/bitstream/Kh-PI-Press/13422/1/vestnik_HPI_51_2014_Gapon_Zakonomernosti.pdf repository.kpi.kharkov.ua/

Schmidt, M. W. Baldridge, K. K., Boatz, J. A., Elbert, S. T., Gordon, M. S., Jensen, J. H., Koseki, S., Matsunaga, N., Nguyen, K. A., Su, S., Windus, T. L., Dupuis, M., Montgomery, J. A. (1993). General atomic and molecular electronic structure system. J. Comput. Chem. 14, 1347–1363. doi: 10.1002/jcc.540141112 CrossRef

Szafran M., Karelson M. M., Katritzky A. R., Koput J., Zerner M. C. (1993). Reconsideration of solvent effects calculated by semiempirical quantum chemical methods. J. Comput. Chem. 14(3), 371–377. doi: 10.1002/jcc.540140312 CrossRef

Lee, C., Yang, W., Parr, R. (1988). Development of the ColleSalvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B. 37(2), 785790. doi: 10.1103/PhysRevB.37.785 CrossRef

Becke, A. D. Dencity-functional thermochemistry. III. The rol of exact exchange. J. Chem. Phys. 98, 5648-5652. doi: 10.1063/1.464913 CrossRef

Cossi, M., Scalmani, G., Rega, N., Barone, V. (2002). New developments in the polarizable continuum model for quantum mechanocal and classical calculations on molecules in solution. J. Chem. Phys. 117, 43–54. doi: 10.1063/1.1480445 CrossRef

Cossi, M., Rega, N., Scalmani, G., Barone, V. (2011). Polarizable dielectric model of solvation with inclusion of charge penetration effect. J. Chem. Phys. 114, 5691–5701. doi: 10.1063/1.1354187 CrossRef

Simanova, S. A. (Ed.). (1997). [New reference book for chemists and chemical technologists. (Vol. 7)]. Moscow, Russian Federation: Chimiya. (in Russian).

Sillen, L. G., Martell, A. E. (1964). Stability consonants of Metal ion Complexes. London: Chem. Soc.