Research output: Contribution to journal › Article › peer-review
A novel Nb2S4 complex with a dithiophosphinate ligand : Synthesis, structure and redox properties. / Gushchin, Artem L.; Rogachev, Alexander V.; Fomenko, Iakov S. et al.
In: Polyhedron, Vol. 158, 15.01.2019, p. 458-463.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - A novel Nb2S4 complex with a dithiophosphinate ligand
T2 - Synthesis, structure and redox properties
AU - Gushchin, Artem L.
AU - Rogachev, Alexander V.
AU - Fomenko, Iakov S.
AU - Romashev, Nikolay F.
AU - Nadolinny, Vladimir A.
AU - Abramov, Pavel A.
AU - Laricheva, Yuliya A.
AU - Sokolov, Maxim N.
N1 - Publisher Copyright: © 2018 Elsevier Ltd
PY - 2019/1/15
Y1 - 2019/1/15
N2 - A new diisobutyldithiophosphinate complex, [Nb2S4(S2PiBu2)4] (1), was obtained by a ligand substitution reaction using (Bu4N)4[Nb2S4(NCS)8] and NaS2PiBu2·3H2O. Its crystal structure has been determined. The Nb–Nb distance is 2.9034(7) Å. The cyclic voltammogram (CV) of 1 in dichloromethane exhibits two successive chemically reversible one-electron oxidation waves at +0.55 and +1.10 V (versus Ag/AgCl) attributed to the NbIV/NbV couple. This is the first {Nb2S4} cluster that shows two reversible oxidations. The paramagnetic mixed-valence Nb(IV/V) product of the one-electron oxidation, [Nb2S4(S2PiBu2)4]+ (1+), was generated in situ. The EPR spectrum of 1+ in acetonitrile reveals a 19-line signal arising from the hyperfine interaction between the unpaired electron and two equivalent 93Nb nuclei with I = 9/2, indicating complete delocalization of the unpaired electron over both metal centers. DFT calculations have been performed for the complexes [Nb2S4(S2PMe2)4], [Nb2S4(S2P(OMe)2)4], [Nb2S4(S2CNMe2)4] and [Nb2S4(S2COMe)4] and their single and double oxidized species in order to explain the peculiarities of their redox behavior. The results show that the HOMOs responsible for oxidation have a predominantly metallic character in all cases, but they are significantly more high-lying for the dithiophosphinate and dithiocarbamate complexes, which explains their ability to be oxidized.
AB - A new diisobutyldithiophosphinate complex, [Nb2S4(S2PiBu2)4] (1), was obtained by a ligand substitution reaction using (Bu4N)4[Nb2S4(NCS)8] and NaS2PiBu2·3H2O. Its crystal structure has been determined. The Nb–Nb distance is 2.9034(7) Å. The cyclic voltammogram (CV) of 1 in dichloromethane exhibits two successive chemically reversible one-electron oxidation waves at +0.55 and +1.10 V (versus Ag/AgCl) attributed to the NbIV/NbV couple. This is the first {Nb2S4} cluster that shows two reversible oxidations. The paramagnetic mixed-valence Nb(IV/V) product of the one-electron oxidation, [Nb2S4(S2PiBu2)4]+ (1+), was generated in situ. The EPR spectrum of 1+ in acetonitrile reveals a 19-line signal arising from the hyperfine interaction between the unpaired electron and two equivalent 93Nb nuclei with I = 9/2, indicating complete delocalization of the unpaired electron over both metal centers. DFT calculations have been performed for the complexes [Nb2S4(S2PMe2)4], [Nb2S4(S2P(OMe)2)4], [Nb2S4(S2CNMe2)4] and [Nb2S4(S2COMe)4] and their single and double oxidized species in order to explain the peculiarities of their redox behavior. The results show that the HOMOs responsible for oxidation have a predominantly metallic character in all cases, but they are significantly more high-lying for the dithiophosphinate and dithiocarbamate complexes, which explains their ability to be oxidized.
KW - Cyclic voltammetry
KW - Dinuclear clusters
KW - EPR
KW - Mixed-valence complexes
KW - Niobium
KW - ENERGY
KW - NIOBIUM
KW - VANADIUM
KW - SERIES
KW - APPROXIMATION
KW - CLUSTERS
KW - ELECTRONIC-STRUCTURE
UR - http://www.scopus.com/inward/record.url?scp=85057568892&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2018.11.035
DO - 10.1016/j.poly.2018.11.035
M3 - Article
AN - SCOPUS:85057568892
VL - 158
SP - 458
EP - 463
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
ER -
ID: 17669169