Dinuclear Vanadium Sulfide Clusters: Synthesis, Redox Behavior, and Magnetic Properties

Iakov S. Fomenko, Artem L. Gushchin, Vladimir A. Nadolinny, Nikolay N. Efimov, Yuliya A. Laricheva, Maxim N. Sokolov

Результат исследования: Научные публикации в периодических изданияхстатья

5 Цитирования (Scopus)

Аннотация

The complex [V2S4(nBu2dtc)4] (1) (dtc = dithiocarbamate) was prepared by a self-assembly reaction from [VO(nBu2dtc)3] and H2S. 1H, 13C, and 51V NMR spectra indicate the presence in solution of two isomers (centrosymmetric and non-centrosymmetric) with different relative orientations of the dithiocarbamate chelate rings. Thermogravimetric studies of 1 show that the thermolysis products are VS2 (in He) or VS (in H2). The cyclic voltammogram (CV) in dichloromethane reveals a chemically reversible one-electron oxidation at +0.61 V followed by an irreversible oxidation at +1.51 V (vs. Ag/AgCl). The redox processes can be attributed to V-centered oxidation. This interpretation is supported by DFT calculations, indicating the predominantly V–V bonding character of the HOMO in both cases. The removal of one electron from the HOMO causes weakening of the V–V bond in 1+. The mixed-valence V(IV/V) product of the one-electron oxidation, [V2S4(nBu2dtc)4](BF4) {[1](BF4)}, was isolated from the reaction with NOBF4 and characterized by elemental analysis, IR spectroscopy, mass spectrometry (ESI-MS), CV, EPR spectroscopy, and magnetochemistry. The EPR spectrum of [1](BF4) in dichloromethane exhibits a single 15-line signal arising from the hyperfine interaction between the unpaired electron and two equivalent 51V nuclei with I = 7/2, indicating complete delocalization of the unpaired electron over both metal centers. The magnetic behavior of [1](BF4) confirms the presence of one unpaired electron and the mixed-valence V(IV/V) oxidation state without any significant magnetic exchange interactions between the paramagnetic complexes.

Язык оригиналаанглийский
Страницы (с-по)2965-2971
Число страниц7
ЖурналEuropean Journal of Inorganic Chemistry
Том2018
Номер выпуска25
DOI
СостояниеОпубликовано - 6 июл 2018

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