Homoleptic Tris(dithiolene) and Tetrakis(dithiolene) Complexes of Uranium(IV)
| Autor: | Marc Fourmigué, Mathieu Roger, Michel Ephritikhine, Thérèse Arliguie, Pierre Thuéry |
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| Rok vydání: | 2005 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 44:594-600 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic049054q |
| Popis: | Reaction of UCl4 with 3 or 4 mol equiv of Na2dddt (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) in THF afforded the first example of a tetrakis(dithiolene) metal compound, [Na4(THF)8U(dddt)4](infinity) (1). The red crystals of 1 are composed of infinite zigzag chains in which Na2(micro-THF)3 fragments ensure the linking of Na2(THF)5U(dddt)4 moieties; the uranium atom is in a dodecahedral environment of eight sulfur atoms. Treatment of UCl4 with 3 mol equiv of Na2dddt in pyridine gave a mixture of tris- and tetrakis(dithiolene) compounds. After addition of 18c6 (18-crown-6), only the tris(dithiolene) complex was obtained and crystallized as orange crystals of [Na(18c6)(py)2]2[U(dddt)3].2py (2.2py) in which the isolated [U(dddt)3]2- anion adopts a slightly distorted trigonal prismatic configuration. A few red crystals of the unsolvated complex 2 and the trinuclear anionic compound [Na(18c6)(py)2]3[Na{U(dddt)3}2] (3) were also obtained along with orange crystals of 2.2py. All the tris(dithiolene) compounds exhibit large folding of the dddt ligand and significant interaction between the C=C double bond and the metal center. |
| Databáze: | OpenAIRE |
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