Oxidation of uranium() thiocyanate complexes: cation-cation interactions in mixed-valent uranium coordination chains
Oxidation of Cs 4 [U(NCS) 8 ] in MeCN or DMF affords structurally characterised examples of the mixed-valent U IV/VI compound Cs 14 [{U(NCS) 8 } 3 {UO 2 (NCS) 4 (H 2 O)}]·4.5H 2 O, or the [U IV -U V -U IV ][U VI ] species [U(DMF) 8 (μ-O)U(NCS) 5 (μ-O)U(DMF) 7 (NCS)][UO 2 (NCS) 5 ]. Vibrational and m...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2019-05, Vol.48 (2), p.674-678 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Online-Zugang: | Volltext |
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| Zusammenfassung: | Oxidation of Cs
4
[U(NCS)
8
] in MeCN or DMF affords structurally characterised examples of the mixed-valent U
IV/VI
compound Cs
14
[{U(NCS)
8
}
3
{UO
2
(NCS)
4
(H
2
O)}]·4.5H
2
O, or the [U
IV
-U
V
-U
IV
][U
VI
] species [U(DMF)
8
(μ-O)U(NCS)
5
(μ-O)U(DMF)
7
(NCS)][UO
2
(NCS)
5
]. Vibrational and magnetism data support their oxidation state formulism, which is further corroborated by computational methodology.
Oxidation of Cs
4
[U(NCS)
8
] in different solvents results in two mixed-valent uranium compounds. Spectroscopic, magnetic and computational data support a unique [U
IV
U
V
U
IV
][U
VI
] oxidation state assignment in [U(DMF)
8
(μ-O)U(NCS)
5
(μ-O)U(DMF)
7
(NCS)][UO
2
(NCS)
5
]. |
|---|---|
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c9dt01005j |