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- Title
New O- and N-N-Bridging Complexes of Tc(V), the Role of the Nitrogen Atom Position in Aromatic Rings: Reaction Mechanism, Spectroscopy, DTA, XRD and Hirshfeld Surface Analysis.
- Authors
Novikov, Anton Petrovich; Volkov, Mikhail Alexandrovich
- Abstract
In this work, O- and N-N-bridging complexes of technetium (V), previously known only for rhenium, were obtained for the first time. Tc(V) complexes with pyridazine (pyd), 1,2,4-triazole (trz), 3,5-dimethylpyrazole (dmpz) and pyrimidine (pyr) were obtained. In three complexes [{TcOCl2}2(μ-O)(μ-pyd)2], [{TcOCl2}2(μ-O)(μ-trz)2]·Htrz·Cl and [{TcO(dmpz)4}(μ-O)(TcOCl4)] two technetium atoms are linked by a Tc-O-Tc bond, and in the first two, Tc atoms are additionally linked by a Tc-N-N-Tc bond through the nitrogen atoms of the aromatic rings. We determined the role of nitrogen atom position in the aromatic ring and the presence of substituents on the formation of such complexes. For the first time, a reaction mechanism for the formation of such complexes was proposed. This article details the crystal structures of four new compounds. The work describes in detail the coordination of Tc atoms in the obtained structures and the regularities of the formation of crystal packings. The spectroscopic properties of the obtained compounds and their mother solutions were studied. The decomposition temperatures of the described complexes were determined. An assumption was made about the oligomerization of three-bridged complexes based on the results of mass spectrometry. Through the analysis of non-valent interactions in the structures, π-stacking, halogen-π and CH-π interactions were found. An analysis of the Hirshfeld surface for [{TcOCl2}2(μ-O)(μ-pyd)2], [{TcOCl2}2(μ-O)(μ-trz)2] and their rhenium analogues showed that the main contribution to the crystalline packing is made by interactions of the type Hal···H/H···Hal (45.4–48.9%), H···H (10.2–15.8%), and O···H/H···O (9.4–16.5%).
- Subjects
SURFACE analysis; ATOMS; NITROGEN; MASS spectrometry; SPECTROMETRY; PYRIDAZINES; COMPOSITION of breast milk
- Publication
International Journal of Molecular Sciences, 2022, Vol 23, Issue 22, p14034
- ISSN
1661-6596
- Publication type
Article
- DOI
10.3390/ijms232214034