Research output: Contribution to journal › Article › peer-review
Dinuclear Vanadium Sulfide Clusters : Synthesis, Redox Behavior, and Magnetic Properties. / Fomenko, Iakov S.; Gushchin, Artem L.; Nadolinny, Vladimir A. et al.
In: European Journal of Inorganic Chemistry, Vol. 2018, No. 25, 06.07.2018, p. 2965-2971.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Dinuclear Vanadium Sulfide Clusters
T2 - Synthesis, Redox Behavior, and Magnetic Properties
AU - Fomenko, Iakov S.
AU - Gushchin, Artem L.
AU - Nadolinny, Vladimir A.
AU - Efimov, Nikolay N.
AU - Laricheva, Yuliya A.
AU - Sokolov, Maxim N.
N1 - Publisher Copyright: © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/7/6
Y1 - 2018/7/6
N2 - 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.
AB - 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.
KW - Cyclic voltammetry
KW - Dithiocarbamates
KW - EPR
KW - Magnetochemistry
KW - Mixed-valent complexes
KW - Sulfide clusters
KW - Vanadium
KW - NIOBIUM
KW - COMPLEXES
KW - REACTIVITY
KW - CHALCOGENIDE CLUSTERS
KW - LIGANDS
KW - ELECTRONIC-STRUCTURE
UR - http://www.scopus.com/inward/record.url?scp=85049567710&partnerID=8YFLogxK
U2 - 10.1002/ejic.201800449
DO - 10.1002/ejic.201800449
M3 - Article
AN - SCOPUS:85049567710
VL - 2018
SP - 2965
EP - 2971
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 25
ER -
ID: 14405216