Abstract
Synthetic approach have been developed, and different-metal coordination compounds [M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O (H4Edta is ethylenediaminetetraacetic acid, bipy is 2,2’-bipyridine, M = Mn(II), n=5 (1); Co(II), n=7 (2); Ni(II), n=7 (3); Cu(II), n=4 (4); Zn(II), n=5 (5)) have been prepared, their comprehensive characterization has been carried out using modern physicochemical methods (elemental analysis, IR spectroscopy, mass spectrometry, and thermogravimetry), and structural features of new complexes have been determined. The synthesised complexes were found to be heteronuclear. The coordination polyhedron of the germanium(IV) remains analogous to that in the structurally characterized ethylenediaminetetraacetatogermanic acid, [Ge(OH)(HEdta)]·H₂O, adopting a distorted octahedral geometry formed by coordination to one hydroxyl group, three carboxylate oxygen atoms, and two nitrogen atoms of the Edta-ligand. The 3d metal center exhibits a coordination number of six, and it is bonded to two oxygen atoms of the carboxylate groups from two germanium-containing complex anions and four nitrogen atoms from two bipyridine molecules.
References
Trunova O. The role of chelate coordination compounds of biogenic metals in the vital activity of plants. Ukr. Chem. J. 2022. 88(12): 91–138.
DOI: 10.33609/2708-129x.88.12.2022.91-138
Nowack B. Environmental Chemistry of Aminopolycarboxylate Chelating Agents. Environ. Sci. Technol. 2002. 36(19): 4009–4016.
DOI: 10.1021/es025683s
Ćendić M., Deeth R. J., Meetsma A., Garribba E., Sanna D., Matović Z. D. Chelating properties of EDTA-type ligands containing six-membered backbone ring toward copper ion: Structure, EPR and TD-DFT evaluation. Polyhedron. 2017. 124: 215–228. DOI: 10.1016/j.poly.2016.12.025
Foreman M. M., Alessio M., Krylov A. I., Weber J. M. Influence of Transition Metal Electron Configuration on the Structure of Metal–EDTA Complexes. J. Phys. Chem. A. 2023. 127(10): 2258–2264.
DOI: 10.1021/acs.jpca.2c07996
Mudsainiyan R. K., Jassal A. K., Chawla S. K. New water soluble heterometallic complex showing unpredicted coordination modes of EDTA. J. Solid State Chem. 2015. 230: 61–69.
DOI: 10.1016/j.jssc.2015.04.001
Stavila V., Wignacourt J.-P., Holt E. M., Conflant P., Drache M., Gulea A. Synthesis and structure of some Co(III)-Bi(III) heterometallic complexes: [Co(NH3)5NCS][Bi(Edta)]2·4H2O, trans-[Co(NH3)4(NO2)2][Bi(Edta)(H2O)]·2H2O,
and [Co(NH3)4(CO3)][Bi(Edta)]·3H2O. Inorg. Chim. Acta. 2003. 353: 43–50.
DOI: 10.1016/s0020-1693(03)00225-1
Stavila V., Gulea A., Shova S., Simonov Y. A., Petrenko P., Lipkowski J., Riblet F., Helm L. An unexpected influence of the nature of the amine on the crystal structure of some
Co(III)–Bi(III) heterobimetallic complexes. Inorg. Chim. Acta. 2004. 357(7): 2060–2068.
DOI: 10.1016/j.ica.2004.01.025
Trunova E., Mishchenko A., Makotryk T. Synthesis and spectral characteristics of heterometallic complexes of Pr(III) with Zn(II), Co(II) based on ethylenediaminetetraacetic and ethylenediaminedisuccinic acids. Ukr. Chem. J. 2021. 87(3): 3–17.
DOI: 10.33609/2708-129x.87.03.2021.3-17 (іn Ukrainian).
Smerigan A., Biswas S., Vila F. D., Hong J., Perez-Aguilar J., Hoffman A. S., Greenlee L., Getman R. B., Bare S. R. Aqueous Structure of Lanthanide–EDTA Coordination Complexes Determined by a Combined DFT/EXAFS Approach. Inorg. Chem. 2023. 62(36): 14523–14532.
DOI: 10.1021/acs.inorgchem.3c01334
Loubalová I., Kopel P. Coordination Compounds of Cu, Zn, and Ni with Dicarboxylic Acids and N Donor Ligands, and Their Biological Activity: A Review. Molecules. 2023. 28(3): 1445.
DOI: 10.3390/molecules28031445
Valdéz-Camacho J. R., Ramírez-Solís A., Escalante J., Ruiz-Azuara L., Hô M. Theoretical determination of half-wave potentials for phenanthroline-, bipyridine-, acetylacetonate-, and glycinate-containing copper (II) complexes. J. Mol. Model. 2020. 26(7): 191.
DOI: 10.1007/s00894-020-04453-x
Seifullina I. I., Martsynko Е. E. Homo- and heterometallic complexonates of germanium(IV). 2011. Odesa. Feniks. (іn Russian).
Seifullina I. I., Martsynko O. E., Chebanenko O. A., Pesaroglo A. G., Pozharitsky O. P. Ammonium ethylenediaminetetraacetategermanate(IV) with growth-stimulating activity (UA Patent No. 121794). Ukraine. 2020. (іn Ukrainian).
Pechinka D. M., Finik О. A., Pesaroglo O. G., Fadieiev Y. M., Seifullina I. I., Martsynko O. E. Onium diaminotetracarboxylates of Germanium(IV): synthesis, structure, applications. Visn. Odes. nac. univ., Him. 2024. 29(2): 37–49.
DOI: 10.18524/2304-0947.2024.2(88).322128
Seifullina I. I., Martsinko E. E., Chebanenko O. A., Dyakonenko V. V., Shishkina S. V., Pesaroglo A. G. Synthesis, molecular and crystal structure of a heterometallic Cu(II)–Ge(IV) complex with 2-hydroxy-1,3-diaminopropane-N,N,N’,N’-tetracetic acid and 2,2’-bipyridine. Voprosy Khimii i Khimicheskoi Tekhnologii. 2020. (6): 159–164.
DOI: 10.32434/0321-4095-2020-133-6-159-164 (іn Ukrainian).
Bellamy L. J. The Infra-red Spectra of Complex Molecules, Springer, Netherlands, Dordrecht, 1975.
DOI: 10.1007/978-94-011-6017-9
Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, Applications in Coordination, Organometallic, and Bioinorganic Chemistry, John Wiley, New York, 2009.
