Heteroligand copper(II), nickel(II), and cobalt(II) complexes with isonicotinic acid hydrazide and L-histidine

N.V. Troshanin^*, T.I. Bychkova^**

Kazan Federal University, Kazan, 420008 Russia

E-mail: ^*nikita-vt@mail.ru, ^**Tamara.Bychkova@kpfu.ru

Received December 25, 2020

ORIGINAL ARTICLE

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DOI: 10.26907/2542-064X.2021.1.45-60

For citation: Troshanin N.V., Bychkova T.I. Heteroligand copper(II), nickel(II), and cobalt(II) complexes with isonicotinic acid hydrazide and L-histidine. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2021, vol. 163, no. 1, pp. 45–60. doi: 10.26907/2542-064X.2021.1.45-60. (In Russian)

Abstract

Complex formation in the ternary systems copper(II)/nickel(II)/cobalt(II) – isonicotinic acid hydrazide – L-histidine was studied by the methods of spectrophotometry and mathematical modeling in an aqueous solution with 0.1 mol dm^–3 KNO₃ as a background electrolyte. The compositions, formation constants, and spectral parameters of the heteroligand complexes with a metal/hydrazide/amino acid ratio of 1:1:1 were determined. It was found that the heteroligand complexes with the neutral form of isonicotinic acid hydrazide have higher stability values than those with the protonated form. The stability of bis- and tris-complexes of the same composition in the series copper(II) – nickel(II) – cobalt(II) is in agreement with the Irving–Williams order. Three isomers of the heteroligand complex of nickel(II) with the protonated form of isonicotinic acid hydrazide and histidine zwitterion were optimized by the method of molecular   mechanics. In the system with cobalt(II), a reversible interaction with atmospheric oxygen was revealed.

Keywords: spectrophotometry, pH-metry, mathematical modeling, complex formation, copper(II), nickel(II), cobalt(II), isonicotinic acid hydrazide, L-histidine

Acknowledgments. We are grateful to E.M. Gilyazetdinov, Candidate of Chemistry, for his help in the pH-metric titrimetry of isonicotinic acid hydrazide using a Basic Titrino 794 automatic titrator (Metrohm) and in determining the dissociation constants of this ligand at the background of 0.1 M KNO₃.

Figure Captions

Fig. 1. Histidine structure.

Fig. 2. Electronic absorption spectra of solutions at various pH values in the systems: a – copper(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – H₂O, c_Cu(II) = 1.0?10^–2 M, c_L = 2.2?10^–2 M, c_HisH = 2.2?10^–2 M; b – nickel(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – H₂O, c_Ni(II) = 5.0?10^–2 M, c_L = 1.2?10^–1 M, c_HisH = 1.2?10^–1 M; T = 25.0 ?С.

Fig. 3. Dependence of the extinction coefficient (ε) on pH for the systems: а – copper(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О (1 – c_Cu(II) = 1.0?10^–2 M, c_L = 1.2?10^–2 M, c_HisH = 1.2?10^–2 M, λ 659 nm; 2 – c_Cu(II) = 1.0?10^–2 M, c_L = 2.2?10^–2 M, c_HisH = 2.2?10^–2 M, λ 628 nm; 3 – c_Cu(II) = 1.6?10^–2 M, c_L = 8.0?10^–3 M, c_HisH = 8.0?10^–3 M, λ 736 nm), b – nickel(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О (1 – c_Ni(II) = 5.1?10^–2 M, c_L = 6.0?10^–2 M, c_HisH =
6.0?10^–2 M, λ 611 nm; 2 – c_Ni(II) = 5.1?10^–2 M, c_L = 1.2?10^–1 M, c_HisH = 1.2?10^–1 M; λ 584 nm; 3 – c_Ni(II) = 1.4?10^–1 M, c_L = 6.0?10^–2 M, c_HisH = 6.0?10^–2 M, λ 640 nm); ℓ = 1.0 cm, T = 25.0 ?С.

Fig. 4. Shared distribution diagrams of the complex forms in the systems: a – copper(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О, c_Cu(II) = 1.0?10^–2 M, c_L = 1.2?10^–2 M, c_HisH = 1.2?10^–2 M   (1 – Cu²⁺, 2 – [CuLH]³⁺, 3 – [CuL]²⁺, 4 – [CuL₂]²⁺, 5 – [CuHisH]²⁺, 6 – [Cu(LH)HisH]³⁺, 7 – [Cu(L)HisH]²⁺); a – nickel(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О; c_Ni(II) = 5.1?10^–2M, c_L = 6.0?10^–2 M, c_HisH = 6.0?10^–2 M (1 – Ni²⁺, 2 – [NiLH]³⁺, 3 – [NiL]²⁺, 4 – [Ni(LH)L]³⁺, 5 – [NiHis]⁺, 6 – [Ni(LH)HisH]³⁺, 7 – [Ni(L)HisH]²⁺); T = 25.0 ?С.

Fig. 5. Isometric structures of the complex [Ni(LН)HisH]³⁺ optimized by the method of molecular mechanics in the model of the MM2 field.

Fig. 6. Dependence of the extinction coefficient (ε) on pH for the systems cobalt(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О: 1 – series 1:1:1; 2 – series 1:2:2; T = 25.0 ?С.

Fig. 7. Time-related changes in the extinction coefficient (a) and spectra (b) of the solution cobalt(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О with different oxygen saturation; c_Cu(II) = 2.2?10^–2 M, c_L = 2.4?10^–2 M, c_HisH = 2.4?10^–2 M; T = 25.0 ?С.

Fig. 8. Electronic absorption spectra of solutions at various pH values (a) and dependence of the extinction coefficient at λ 503 nm on pH (b) in the system cobalt(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О; c_Co(II) = 3.0?10^–2 M, c_L = 1.4?10^–2 M, c_HisH = 1.4?10^–2 M; T = 25.0 ?С.

Fig. 9. Shared distribution diagram of the complex forms in the system cobalt(II) – isonicotinic acid hydrazide (L) – L-histidine (HisH) – Н₂О; c_Co(II) = 3.0?10^–2 M, c_L = 1.4?10^–2 M, c_HisH = 1.4?10^–2 M;
1 – Co²⁺, 2 – [CoLH]³⁺, 3 – [CoL]²⁺, 4 – [CoHisH]²⁺, 5 – [Co(LH)HisH]³⁺, 6 – [Co(L)HisH]²⁺; T = 25.0 ?С.

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