Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Novel Synthesis Methods of New Imidazole-Containing Coordination Compounds and Salts Tc(IV, V, VII) – Reaction Mechanism, XRD and Hirshfeld Surface Analysis

Mikhail Alexandrovich Volkov
* ORCID logo ,
Anton Petrovich Novikov
ORCID logo ,
Mikhail Semenovich Grigoriev
ORCID logo ,
Alexander Mikhailovich Fedoseev
,
Konstantin Eduardovich German
ORCID logo
Version 1 : Received: 31 July 2022 / Approved: 3 August 2022 / Online: 3 August 2022 (03:29:49 CEST)

A peer-reviewed article of this Preprint also exists.

Volkov, M.A.; Novikov, A.P.; Grigoriev, M.S.; Fedoseev, A.M.; German, K.E. Novel Synthesis Methods Of New Imidazole-Containing Coordination Compounds Tc(IV, V, VII)—Reaction Mechanism, Xrd And Hirshfeld Surface Analysis. Int. J. Mol. Sci. 2022, 23, 9461. Volkov, M.A.; Novikov, A.P.; Grigoriev, M.S.; Fedoseev, A.M.; German, K.E. Novel Synthesis Methods Of New Imidazole-Containing Coordination Compounds Tc(IV, V, VII)—Reaction Mechanism, Xrd And Hirshfeld Surface Analysis. Int. J. Mol. Sci. 2022, 23, 9461.

Abstract

In this work, we have proposed two new methods for the synthesis of [TcO2L4]+ (where L = im-idazole (Im), methylimidazole (MeIm)) complexes using thiourea (Tu) and Sn(II) as reducing agents. The main and by-products of the reactions were determined, and possible reaction mechanisms were proposed. We have shown that the reduction of Tc(VII) with thiourea is ac-companied by the formation of the Tc(III) intermediate and further oxidation to Tc(V). The reac-tion conditions changing can lead to the formation of Tc(VII) and Tc(IV) salts. Seven new crystal structures are described in this work: Tc(V) complexes, salts with Tc(VII) and Tc(IV) anions. For halide salts of Tu the cell parameters were determined. In all obtained compounds, except for [TcO2(MeIm)4]TcO4, there are π-stacking interactions between aromatic rings. An increase in the anion size lead to weaken intermolecular interactions. Halogen bonds and anion-π interactions have also been found in hexahalide-containing compounds. The Hirshfeld surface analysis showed that the main contribution to the crystal packing is made by van der Waals interactions of the H···H type (42.5–55.1%), H···C/C ···H (17.7–21.3%) and hydrogen bonds, which contribute 15.7–25.3% in total.

Keywords

technetium; imidazole; technetyl; XRD-analysis; Hirshfeld surface analysis; π-interactions; met-al-nitrogen bond; supramolecular chemistry

Subject

Chemistry and Materials Science, Inorganic and Nuclear Chemistry

Copyright: This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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