Homoleptic Tris(dithiolene) and Tetrakis(dithiolene) Complexes of Uranium(IV)
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- 作者：Mathieu Roger ; Thé ; rè ; se Arliguie ; Pierre Thué ; ry ; Marc Fourmigué ; and Michel Ephritikhine
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：February 7, 2005
- 年：2005
- 卷：44
- 期：3
- 页码：594 - 600
- 全文大小：239K
- 年卷期：v.44,no.3(February 7, 2005)
- ISSN：1520-510X
文摘
Reaction of UCl4 with 3 or 4 mol equiv of Na2dddt (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) in THF affordedthe first example of a tetrakis(dithiolene) metal compound, [Na4(THF)8U(dddt)4]
(1). The red crystals of 1 arecomposed of infinite zigzag chains in which Na2(
-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 ofNa2dddt 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 fewred 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 ofthe dddt ligand and significant interaction between the C=C double bond and the metal center.
(1). The red crystals of 1 arecomposed of infinite zigzag chains in which Na2(-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 ofNa2dddt 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 fewred 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 ofthe dddt ligand and significant interaction between the C=C double bond and the metal center.