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

ABSTRACT: In this work, we have proposed two new methods for the synthesis of [TcO₂L₄]⁺ (where L = imidazole (Im), methylimidazole (MeIm)) complexes using thiourea (Tu) and Sn(II) as the 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 accompanied by the formation of the Tc(III) intermediate and further oxidation to Tc(V). The reaction 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 the halide salts of Tu the cell parameters were determined. In all of the obtained compounds, except for [TcO₂(MeIm)₄]TcO₄, there are π-stacking interactions between the aromatic rings. An increase in the anion size lead to weakening of the intermolecular interactions. The halogen bonds and anion-π interactions were also found in the hexahalide-containing compounds. The Hirshfeld surface analysis showed that the main contribution to the crystal packing is created by the 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.

SUBMITTER: Volkov MA

PROVIDER: S-EPMC9408894 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

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

Volkov Mikhail Alexandrovich MA Novikov Anton Petrovich AP Grigoriev Mikhail Semenovich MS Fedoseev Alexander Mikhailovich AM German Konstantin Eduardovich KE

International journal of molecular sciences 20220821 16

In this work, we have proposed two new methods for the synthesis of [TcO2L4]+ (where L = imidazole (Im), methylimidazole (MeIm)) complexes using thiourea (Tu) and Sn(II) as the 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 accompanied by the formation of the Tc(III) intermediate and further oxidation to Tc(V). The reaction con ...[more]

PMID: 36012725

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Project description:Two coordination compounds containing tetra-n-butyl-ammonium cations and bis-tfd-chelated molybdenum(IV) [tfd2- = S2C2(CF3)22-] and oxalate (ox2-, C2O42-) in complex anions are reported, namely bis-(tetra-n-butyl-ammonium) bis-(1,1,1,4,4,4-hexa-fluoro-but-2-ene-2,3-di-thiol-ato)oxalatomolybdate(IV)-chloro-form-oxalic acid (1/1/1), (C16H36N)2[Mo(C4F6S2)2(C2O4)]·CHCl3·C2H2O4 or (N n Bu4)2[Mo(tfd)2(ox)]·CHCl3·C2H2O4, and bis-(tetra-n-butyl-ammonium) μ-oxalato-bis-[bis-(1,1,1,4,4,4-hexa-fluoro-but-2-ene-2,3-di-thiol-ato)molybdate(IV)], (C16H36N)2[Mo2(C4F6S2)4(C2O4)] or (N n Bu4)2[(tfd)2Mo(μ-ox)Mo(tfd)2]. They contain a terminal oxalate ligand in the first compound and a bridging oxalate ligand in the second compound. Anion 12- is [Mo(tfd)2(ox)]2- and anion 22-, formally generated by adding a Mo(tfd)2 fragment onto 12-, is [(tfd)2Mo(μ-ox)Mo(tfd)2]2-. The crystalline material containing 12- is (N n Bu4)2-1·CHCl3·oxH2, while the material containing 22- is (N n Bu4)2-2. Anion 22- lies across an inversion centre. The complex anions afford a rare opportunity to compare terminal oxalate with bridging oxalate, coordinated to the same metal fragment, here (tfd)2MoIV. C-O bond-length alternation is observed for the terminal oxalate ligand in 12-: the difference between the C-O bond length involving the metal-coordinating O atom and the C-O bond length involving the uncoordinating O atom is 0.044 (12) Å. This bond-length alternation is significant but is smaller than the bond-length alternation observed for oxalic acid in the co-crystallized oxalic acid in (N n Bu4)2-1·CHCl3·oxH2, where a difference (for C=O versus C-OH) of 0.117 (14) Å was observed. In the bridging oxalate ligand in 22-, the C-O bond lengths are equalized, within the error margin of one bond-length determination (0.006 Å). It is concluded that oxalic acid contains a localized π-system in its carb-oxy-lic acid groups, that the bridging oxalate ligand in 22- contains a delocalized π-system and that the terminal oxalate ligand in 12- contains an only partially localized π-system. In (N n Bu4)2-1·CHCl3·oxH2, the F atoms of two of the -CF3 groups in 12- are disordered over two sets of sites, as are the N and eight of the C atoms of one of the N n Bu4 cations. In (N n Bu4)2-2, the whole of the unique N n Bu4+ cation is disordered over two sets of sites. Also, in (N n Bu4)2-2, a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18].

Dataset Information

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

Publications

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

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