Salmon Lionel, Thuéry Pierre, Asfari Zouhair, Ephritikhine Michel
Service de Chimie Moléculaire, DSM, DRECAM, CNRS URA 331, CEA Saclay, 91191, Gif-sur-Yvette, France.
Dalton Trans. 2006 Jun 28(24):3006-14. doi: 10.1039/b601237j. Epub 2006 Mar 27.
Reactions of UCl4 with 25,27-dimethoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (H2Me2calix) in THF or pyridine at 80 degrees C gave [UCl2(Me2calix)L2] [L = THF (1) or pyridine (2)]. Similar treatment of U(acac)(4) (acac = MeCOCHCOMe) with H2Me2calix in THF or pyridine afforded [U(acac)2(Me2calix)] (3). The bis-calixarene compound [U(Me2calix)(H2calix)] (4) was obtained by reaction of U(OTf)4 or U(OTf)3 with H2Me2calix in pyridine at 110 degrees C. Treatment of UCl4 with H2Me2calix in pyridine at 110 degrees C gave [Mepy][UCl2(Hcalix)(py)2] (5) resulting from demethylation and acid cleavage of the methoxy groups of the calixarene ligand of 2. Adventitious traces of air were responsible for the formation of [Hpy][Mepy]4[{UCl(calix)}3(mu3-O)][UCl6] (6) during the reaction of UCl4 and H2Me2calix, and of [{U(Me2calix)(mu3-O)LiCl(THF)}2] (7) during the reaction of 2 with tBuLi. The X-ray crystal structures of 1.2THF, 2.2py, 3.0.25L (L = THF and py), 4.2py, 5, 6.3py and 7.THF have been determined.
四氯化铀与25,27 - 二甲氧基 - 5,11,17,23 - 四 - 叔丁基杯[4]芳烃（H₂Me₂杯芳烃）在四氢呋喃或吡啶中于80℃反应，生成了[UCl₂(Me₂杯芳烃)L₂] [L = 四氢呋喃 (1) 或吡啶 (2)]。在四氢呋喃或吡啶中，用H₂Me₂杯芳烃对乙酰丙酮铀（acac = MeCOCHCOMe）进行类似处理，得到了[U(acac)₂(Me₂杯芳烃)] (3)。双杯芳烃化合物[U(Me₂杯芳烃)(H₂杯芳烃)] (4) 通过四氟甲磺酸铀(IV)或三氟甲磺酸铀(III)与H₂Me₂杯芳烃在吡啶中于110℃反应制得。在吡啶中于110℃用H₂Me₂杯芳烃处理四氯化铀，得到了[Mepy][UCl₂(H杯芳烃)(py)₂] (5)，它是由2中杯芳烃配体的甲氧基去甲基化和酸裂解产生的。在四氯化铀与H₂Me₂杯芳烃的反应过程中，空气中偶然存在的痕量氧气导致了[Hpy][Mepy]₄[{UCl(杯芳烃)}₃(μ₃ - O)][UCl₆] (6) 的形成，而在2与叔丁基锂的反应过程中则形成了[{U(Me₂杯芳烃)(μ₃ - O)LiCl(四氢呋喃)}₂] (7)。已测定了1·2四氢呋喃、2·2吡啶、3·0.25L（L = 四氢呋喃和吡啶）、4·2吡啶、5、6·3吡啶和7·四氢呋喃的X射线晶体结构。
