Homo- and Heteroligand Nickel(II) Complexes with Benzoic and para-Methoxybenzoic Acid Hydrazides and L-Histidine

N.V. Troshanin, А.А. Razryvina, E.M. Gilyazetdinov, T.I. Bychkova^*, V.G. Shtyrlin

Kazan Federal University, Kazan, 420008 Russia

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

Received January 24, 2017

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Abstract

Complex formation of nickel(II) with benzoic, para-methoxybenzoic acid hydrazides, and L-histidine have been studied by the methods of pH-metric titrimetry, spectrophotometry, and mathematical modelling in aqueous solutions with 1.0 mol dm^–3 KNO₃ as background at 298 K. Dissociation constants of ligands, as well as composition, formation constants, and spectral parameters of homo- and heteroligand complexes have been determined. It has been shown that stability of the complexes formed with para-methoxybenzoic acid hydrazide is higher than with benzoic acid hydrazide, which is consistent with the electron-donor properties of the methoxy group. Extra stabilization of the nickel(II) heteroligand complexes with benzoic (para-methoxybenzoic) acid hydrazide and L-histidine has been discovered and interpreted.

Keywords: pH-metry, spectrophotometry, mathematical modelling, complex formation, nickel(II), benzoic acid hydrazide, para-methoxybenzoic acid hydrazide, L-histidine

Figure Captions

Fig. 1. Dependences of Bjerrum function (n) on pH for the following systems: 1 – benzoic acid hydrazide (L) – Н₂О – 0.1 М KNO₃, с_L = 1.010^–2 М; 2 – para-methoxybenzoic acid hydrazide (L') – Н₂О – 0.1 М KNO₃, с_L' = 1.010^–2 М.

Fig. 2. Dependence of Bjerrum function (n) on pH for the system L-histidine (HisH) – Н₂О – 0.1 М KNO₃, c_HisH = 1.010^–2 М.

Fig. 3. Diagrams of sharing of the protonated and molecular forms of hydrazides in the systems: a – benzoic acid hydrazide (L) – Н₂О – 0.1 М KNO₃, c_L = 1.010^–2 М; b – para-methoxybenzoic acid hydrazide (L') – Н₂О – 0.1 М KNO₃, с_L' = 1.010^–2 М.

Fig. 4. Diagram of sharing of the forms in the system L-histidine (HisH) – Н₂О – 0.1 М KNO₃, c_HisH = 1.010^–2 М; 1 – HisH₃²⁺, 2 – HisH₂⁺, 3 – HisH, 4 – His^–.

Fig. 5. Dependences of Bjerrum function (n) on pH for the following systems: a – nickel(II) – benzoic acid hydrazide (L) – Н₂О – 0.1 М KNO₃, с_Ni(II) = 1.0∙10^–2 М, с_L = 3.0∙10^–2 M; b – nickel(II) – para-methoxybenzoic acid hydrazide (L') – Н₂О – 0.1 М KNO₃, с_Ni(II) = 1.0∙10^–2 М, c_L' = 3.0∙10^–2 M.

Fig. 6. Dependence of Bjerrum function (n) on pH for the system nickel(II) – L-histidine (HisH) – Н₂О – 0.1 М KNO₃, с_Ni(II) = 1.0∙10^–2 М, с_HisH = 3.1∙10^–2 M.

Fig. 7. Diagrams of sharing of the complex forms in the systems: a – nickel(II) – benzoic acid hydrazide (L) – 0.1 M KNO₃ – Н₂О, c_Ni(II) = 1.0∙10^–2 М, c_L = 3.0∙10^–2 M, 1 – Ni²⁺, 2 – NiL²⁺, 3 – NiL₂²⁺, 4 – NiL₃²⁺; b – nickel(II) – para-methoxybenzoic acid hydrazide (L') – 0.1 M KNO₃ – Н₂О, c_Ni(II) = 1.0∙10^–2 М, c_L' = 3.0∙10^–2 M; 1 – Ni²⁺, 2 – Ni(L')²⁺, 3 – Ni(L')₂²⁺, 4 – Ni(L')₃²⁺.

Fig. 8. Diagram of sharing of the complex forms in the system nickel(II) – L-histidine (HisH) – 0.1 M KNO₃ – Н₂О, c_Ni(II) = 1.0∙10^–2 М, c_HisH = 3.1∙10^–2 M; 1 – Ni²⁺, 2 – Ni(HisH)²⁺, 3 – Ni(His)⁺, 4 – Ni(His)(HisH)⁺, 5 – Ni(His)₂, 6 – Ni(His)₃^–.

Fig. 9. Electron absorption spectra of the solutions at various pH values in the system nickel(II) – benzoic acid hydrazide (L) – 0.1 М KNO₃ – H₂O, c_Ni(II) = 9.8∙10^–3 М, c_L = 3.0∙10^–2 M.

Fig. 10. Electron absorption spectra of the solutions at various pH values in the system nickel(II) – para-methoxybenzoic acid hydrazide (L') – 0.1 М KNO₃ – H₂O, c_Ni(II) = 9.7∙10^–3 М, c_L' = 3.0∙10^–2 M.

Fig. 11 Electron absorption spectra of the solutions at various pH values in the system nickel(II) – L-his­tidine (HisH) – 0.1 М KNO₃ – H₂O, c_Ni(II) = 3.0∙10^–2 М, c_HisH = 1.2∙10^–1 M.

Fig. 12. Reconstructed electron spectra of absorption of the complexes in the system nickel(II) – benzoic acid hydrazide (L) – 0.1 М KNO₃ – H₂O, с_Ni(II) = 9.8∙10^–3 М, с_L = 3.0∙10^–2 М; 1 – Ni²⁺, 2 – NiL²⁺, 3 – NiL₂²⁺, 4 – NiL₃²⁺.

Fig. 13. Reconstructed electron spectra of absorption of the complexes in the system nickel(II) – para-methoxybenzoic acid hydrazide (L') – 0.1 М KNO₃ – H₂O, с_Ni(II) = 9.7∙10^–3 М, с_L' = 3.0∙10^–2 М; 1 – Ni²⁺, 2 – Ni(L')²⁺, 3 – Ni(L')₂²⁺, 4 – Ni(L')₃²⁺.

Fig. 14. Reconstructed electron spectra of absorption of the complexes in the system nickel(II) – L-his­tidine (HisH) – 0.1 М KNO₃ – H₂O, с_Ni(II) = 3.0∙10^–2 М, с_HisH = 1.2∙10^–1 М; 1 – Ni²⁺, 2 – Ni(His)⁺, 3 – Ni(HisH)²⁺, 4 – Ni(His)₂.

Fig. 15. Dependences of Bjerrum function (n) on pH for the following systems: a – nickel(II) – benzoic acid hydrazide (L) – L-histidine (HisH) – Н₂О – 0.1 М KNO₃, с_Ni(II) = 9.9∙10^–3 М, с_L = 1.1∙10^–2 M, с_HisН = 1.0∙10^–2 M; b – nickel(II) – para-methoxybenzoic acid hydrazide (L') – L-histidine (HisH) – Н₂О – 0.1 М KNO₃, с_Ni(II)  = 9.9∙10^–3 М, c_L' = 1.0∙10^–2 M, c_HisН = 1.0∙10^–2 M.

Fig. 16. Diagram of sharing of the complex forms in the system nickel(II) – benzoic acid hydrazide (L) – L-histidine (HisH) – H₂O – 0.1 M KNO₃, c_Ni(II) = 9.9∙10^–3 М, c_L = 1.1∙10^–2 M, c_HisH = 1.0∙10^–2 M; 1 – Ni²⁺, 2 – Ni(His)⁺, 3 – Ni(HisH)²⁺, 4 – NiL²⁺, 5 – NiL₂²⁺, 6 – Ni(HisH)L²⁺, 7 – Ni(His)L⁺.

Fig. 17. Diagram of sharing of the complex forms in the system nickel(II) – para-methoxybenzoic acid hydrazide (L') – L-histidine (HisH) – H₂O – 0.1 M KNO₃, c_Ni(II) = 9.9∙10^–3 М, c_L' = 1.0∙10^–2 M, c_HisH = 1.0∙10^–2 M; 1 – Ni²⁺, 2 – Ni(His)⁺, 3 – Ni(His)₂, 4 – Ni(L')²⁺, 5 – Ni(L')₂²⁺, 6 – Ni(HisH)(L')²⁺, 7 – Ni(His)(L')⁺.

Fig. 18. Electron absorption spectra of the solutions at various pH values in the system nickel(II) – benzoic acid hydrazide (L) – L-histidine (HisH) – 0.1 М KNO₃ – H₂O, c_Ni(II) = 5.1∙10^–2 М, c_L = 5.5∙10^–2 M, c_HisH = 5.5∙10^–2 M.

Fig. 19. Electron absorption spectra of the solutions at various pH values in the system nickel(II) – para-methoxybenzoic acid hydrazide (L') – L-histidine (HisH) – 0.1 М KNO₃ – H₂O, c_Ni(II) = 5.1∙10^–2 М, c_L' = 5.5∙10^–2 M, c_HisH = 5.5∙10^–2 M.

Fig. 20. Reconstructed electron absorption spectra of the complexes at various pH values in the system nickel(II) – benzoic acid hydrazide (L) – L-histidine (HisH) – 0.1 М KNO₃ – H₂O, c_Ni(II) = 5.1∙10^–2 М, c_L = 5.5∙10^–2 M, c_HisH = 5.5∙10^–2 M; 1 – Ni²⁺, 2 – Ni(His)₂, 3 – NiL²⁺, 4 – NiL₂²⁺, 5 – Ni(HisH)L²⁺, 6 – Ni(His)L⁺.

Fig. 21. Reconstructed electron absorption spectra of the complexes in the system nickel(II) – para-methoxybenzoic acid hydrazide (L') – L-histidine (HisH) – 0.1 М KNO₃ – H₂O, c_Ni(II) = 5.1∙10^–2 М, c_L' = 5.5∙10^–2 M, c_HisH = 5.5∙10^–2 M; 1 – Ni²⁺, 2 – Ni(L')²⁺, 3 – Ni(L')₂²⁺, 4 – Ni(HisH)(L')²⁺, 5 – Ni(His)(L')⁺.

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For citation: Troshanin N.V., Razryvina А.А., Gilyazetdinov E.M., Bychkova T.I., Shtyrlin V.G. Homo- and heteroligand nickel(II) complexes with benzoic and para-methoxybenzoic acid hydrazides and L-histidine. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2017, vol. 159, no. 1, pp. 40–57. (In Russian)

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