α,ω-Bis­(hydrazidomethylsulfinyl and sulfonyl)alkanes: State in solution and interaction with copper(II)

V.V. Neklyudov a*, G.A. Boos a**, M.M. Shulaeva b***, G.A. Chmutova a****, R.R. Amirov a*****

aKazan Federal University, Kazan, 420008 Russia

bArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Kazan, 420088 Russia

E-mail: *VVNeklyudov@hotmail.com, **Galina.Boos@kpfu.ru, ***mshulaeva@iopc.ru, ****Galina.Tschmutowa@kpfu.ru, *****ramirov@kpfu.ru

Received January 25, 2021


ORIGINAL ARTICLE

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DOI: 10.26907/2542-064X.2021.1.29-44

For citation: Neklyudov V.V., Boos G.A., Shulaeva M.M., Chmutova G.A., Amirov R.R. α,ω-Bis(hydrazidomethylsulfinyl and sulfonyl)alkanes: State in solution and interaction with copper(II). Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2021, vol. 163, no. 1, pp. 29–44. doi: 10.26907/2542-064X.2021.1.29-44. (In Russian)

Abstract

In this paper, the results of our previous findings on the solvent, protolytic, and complexing abilities of α,ω-bis(amido- and hydrazidomethylsulfinyl and sulfonyl)alkanes were summarized and compared. In addition, the most probable structures of copper(II) complexes (mononuclear 1:1 and 1:2, binuclear 2:4) with 1,8-bis(hydrazidomethylsulfonyl)octane and 1,10-bis(hydrazidomethylsulfonyl)decane were characterized by DFT at PBE/6-311G(d) level of theory. 1,8-Bis(hydrazidomethylsulfonyl)octane and 1,10-bis(hydrazidomethylsulfonyl)decane were found to have unfolded conformations and to be coordinated by copper(II) in the amide form like hydrazides of carboxylic acids. In the binuclear complex, all four ligands are bridging and differ in coordination ways, exhibiting the denticity of four, two, and three. It was demonstrated that sulfoxide groups do not take part in coordination.

Keywords: α,ω-Bis(amido- and hydrazidomethylsulfinyl and sulfonyl)alkanes, copper(II), complexation, ligand denticity, three-dimensional structure

Figure Captions

Fig. 1. Optimized structures of compounds: (L1): “unfolded” (a) and “folded” (b) conformations, (L2) (c), (L3) (d), (L4) (e), (L5) (f).

Fig. 2. Optimized three-dimensional structures of [Cu(L3)]2+ (a) and [Cu(L3)2]2+ (b) complexes according to the data in [4].

Fig. 3. Optimized three-dimensional structures of [Cu(L3)]2+ (a) and [Cu(L3)2]2+ (b) complexes according to the data in [4].

Fig. 4. Molecular structure of Cu2(L4)3](NO3)4∙2H2O binuclear complex according to the data of X-ray crystallography in [5]. Nitrate anions and water molecules are not shown for simplification purposes.

Fig. 5. Structure of [Cu2(L5)4]4+ binuclear complex according to the data of quantum-chemical modeling at the PBE/6-311G(d) level.

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