dc.contributor.author |
Gushchin A. |
|
dc.contributor.author |
Rogachev A. |
|
dc.contributor.author |
Fomenko I. |
|
dc.contributor.author |
Romashev N. |
|
dc.contributor.author |
Nadolinny V. |
|
dc.contributor.author |
Abramov P. |
|
dc.contributor.author |
Laricheva Y. |
|
dc.contributor.author |
Sokolov M. |
|
dc.date.accessioned |
2020-01-15T21:17:38Z |
|
dc.date.available |
2020-01-15T21:17:38Z |
|
dc.date.issued |
2019 |
|
dc.identifier.issn |
0277-5387 |
|
dc.identifier.uri |
https://dspace.kpfu.ru/xmlui/handle/net/155571 |
|
dc.description.abstract |
© 2018 Elsevier Ltd 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. |
|
dc.relation.ispartofseries |
Polyhedron |
|
dc.subject |
Cyclic voltammetry |
|
dc.subject |
Dinuclear clusters |
|
dc.subject |
EPR |
|
dc.subject |
Mixed-valence complexes |
|
dc.subject |
Niobium |
|
dc.title |
A novel Nb<inf>2</inf>S<inf>4</inf> complex with a dithiophosphinate ligand: Synthesis, structure and redox properties |
|
dc.type |
Article |
|
dc.relation.ispartofseries-volume |
158 |
|
dc.collection |
Публикации сотрудников КФУ |
|
dc.relation.startpage |
458 |
|
dc.source.id |
SCOPUS02775387-2019-158-SID85057568892 |
|