Synthesis, acid-base, and complexing properties of ethylenediaminetetra(O-alkyl)methylene­phosphonic acids – the closest organophosphorus analogs of ethylenediaminetetraacetic acid

A.R. Garifzyanov*, I.D. Shurygin**, I.I. Mirzayanov***, F.V. Devyatov****

Kazan Federal University, Kazan, 420008 Russia

E-mail: *agar@live.ru, **idshurygin@gmail.com, ***ildar4016@mail.ru, ****feddev54@gmail.com

Received January 17, 2022


ORIGINAL ARTICLE

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DOI: 10.26907/2542-064X.2022.1.5-21

For citation: Garifzyanov A.R., Shurygin I.D., Mirzayanov I.I., Devyatov F.V. Synthesis, acid-base, and complexing properties of ethylenediaminetetra(O-alkyl)methylenephosphonic acids – the closest organophosphorus analogs of ethylenediaminetetraacetic acid. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2022, vol. 164, no. 1, pp. 5–21. doi: 10.26907/2542-064X.2022.1.5-21. (In Russian)

Abstract

A number of new complexones – ethylenediaminetetra(O-alkyl)methylenephosphonic acids, the structurally related organophosphorus analogs of ethylenediaminetetraacetic acid – were synthesized. The acid-base and complexing properties of the obtained substances with alkaline-earth and transition metal ions were studied by the methods of potentiometric titration and mathematical simulation. The following parameters were calculated: the ionization constants of the ligands, the stability and deprotonation constants of their 1:1 complexes with metal ions, and the distribution of the complex forms. The calculated stability constants for H4L-Alk ligands and d-elements follow the Irving–Williams series.

Keywords: complexones, aminophosphonates, EDTA, EDTMP, complexation

Acknowledgements. The study was supported by the Russian Foundation for Basic Research (project no. 20-33-90235).

Figure Captions

Fig. 1. H4EDTA, H8EDTMP, and H4L-Alk structures.

Fig. 2. Dependence of the formation function ñ of the ligands on pH for H4L-Alk and the distribution of the complex forms for H4L-Me.

Fig. 3. Dependence of the formation function ñ of the complexes with alkaline-earth metal ions for H4L-Me and the distribution of the complex forms for the H4L-Me – Ca(II) system.

Fig. 4. Dependence of the formation function ñ of the complexes with transition metal ions for H4L-Me and the distribution of the complex forms for the H4L-Me – Co(II) system.

Scheme 1. Synthesis of potassium salts of ethylenediaminetetra(O-alkyl)methylenephosphonic acids.

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