[(XA2)2ThCl2(dme)] | 927674-69-9

• 英文名称: [(XA2)2ThCl2(dme)]
• 英文别名: [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)2ThCl2(dme)]
• CAS: 927674-69-9
• 化学式: C₅₁H₇₂Cl₂N₂O₃Th
• 分子量: 1064.09
• InChiKey: YVQCUDBVGNZPTQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(XA2)2ThCl2(dme)] 在 苄基氯化镁 作用下， 以 乙醚 为溶剂， 以41%的产率得到
  参考文献：
  名称：

  Divergent reactivity of [(κ3-L)ThCl2(dme)] with Grignard reagents: Alkylation, ancillary ligand transfer to magnesium, and halide exchange caught in the act

  摘要：

  Reaction of [(BDPP)ThCl2(dme)] (1) with 2 equivalents of MeMgBr in OEt2, followed by filtration and layering a toluene solution with hexanes at -30 degrees C yielded a single large crystal of [{(BDPP)ThX (mu-X)(2)Mg(OEt2)(mu-Me)}(2)]center dot 2 toluene (X = Br0.73-0.87/Cl0.13-0.27; 3 center dot 2 toluene). This product is the result of halide exchange to form a partially brominated neutral thorium species, which is adducted with MeMgX(OEt2). The complex is then tetrametallic as a result of Mg-Me-Mg bridges. The structure of complex 3 provides direct insight into the process by which halide exchange takes place between electrophilic metal halide complexes and Grignard reagents. This reactivity stands in stark contrast to the reactions of 1 and [(XA(2))ThCl2(dme)] (2) with PhCH2MgCl. In these cases the expected dialkyl products, [LTh(CH2Ph)(2)] [L = BDPP (4) and XA(2) (5)], were formed under most conditions. However, addition of a PhCH2MgCl solution to 2 at -78 degrees C and warming to room temperature after 5 minutes gave [(XA(2))Mg(dme)] (6), the product of ancillary ligand transfer from thorium to magnesium, in 30 -50% yield. (c) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2010.08.048
• 作为产物：
  描述：

  ThCl₄(DME)₂ 、 K2(dme)2[4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene] 以 甲苯 为溶剂， 以59%的产率得到[(XA2)2ThCl2(dme)]
  参考文献：
  名称：

  Extremely Stable Thorium(IV) Dialkyl Complexes Supported by Rigid Tridentate 4,5-Bis(anilido)xanthene and 2,6-Bis(anilidomethyl)pyridine Ligands

  摘要：

  A new NON-donor ligand, 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene (H-2[XA(2)], 1), was prepared by palladium-catalyzed coupling of 2,6-diisopropylaniline with the appropriate dibromoxanthene precursor. Stable K-2(dme)(2)[XA(2)] (2) and Na-2[XA(2)] (3) salts were accessible by deprotonation of H-2[XA(2)] with KH in dme or NaH in toluene. The thermally unstable lithium salt of McConville's 2,6-bis(2,6-diisopropylanilidomethyl)pyridine ligand (Li-2[BDPP], 4) was isolated by deprotonation with nBuLi or LiCH2SiMe3 in hexanes at low temperature. Reaction of [ThCl4(dme)(2)] with Li-2[BDPP] or M-2(dme)(n)[XA(2)] resulted in the formation of pentagonal bipyramidal [LThCl2(dme)] complexes (L = BDPP, 5; XA(2), 6). Subsequent reaction of 5 or 6 with LiCH2SiMe3 gave base- and salt-free dialkyl complexes, [LTh(CH2SiMe3)(2)] (L = BDPP, 7; XA(2), 8), which are stable for days in solution at 90 and 70 degrees C, respectively. Complexes 5, 7, and 8 were also accessible by initial combination of 2 or 4 equiv of LiCH2SiMe3 with [ThCl4(dme)(2)], followed by addition of H2L. These reactions likely proceed by alkane elimination, but dialkyl or tetraalkyl thorium intermediates were not identified. The X-ray crystal structure of 8 suggests the presence of alpha-agostic C-H-Th interactions for both alkyl groups. In solution, 7 and 8 exhibit temperature-dependent (1)J(C,H) coupling constants for ThCH2, demonstrating the presence of alpha-agostic interactions which become increasingly favored at lower temperature. Reaction of 5 with Li-2[BDPP] at 0 degrees C or 7 with H-2[BDPP] at 100 degrees C resulted in the formation of extremely sterically encumbered [Th(BDPP)(2)] (9), which adopts a highly distorted six-coordinate geometry with the four anilido groups arranged in an approximate tetrahedron around thorium. Bis-ligand complexes were not accessible with the XA(2) platform, presumably due to increased ligand rigidity.

  DOI：

  10.1021/om060914f

文献信息

• Single and Double Alkyl Abstraction from a Bis(anilido)xanthene Thorium(IV) Dibenzyl Complex: Isolation of an Organothorium Cation and a Thorium Dication
  作者：Carlos A. Cruz、David J. H. Emslie、Laura E. Harrington、James F. Britten

  DOI：10.1021/om7011503

  日期：2008.1.1

  Reaction of [(XA2)ThCl2(dme)] [XA2 = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene] with 2 equiv of PhCH2MgCl resulted in the formation of solvent-free [(XA2)Th(CH2Ph)2] (1). Subsequent reaction of 1 with either 1 or 2 equiv of B(C6F5)3 allowed isolation of the first non-cyclopentadienyl actinide alkyl cation, [(XA2)Th(CH2Ph)][PhCH2B(C6F5)3] (2), and a rare example of an actinide

  [（XA 2）ThCl 2（dme）] [XA 2 = 4,5-双（2,6-二异丙基苯胺基）-2,7-二叔丁基-9,9-二甲基x吨]与2当量的PhCH 2 MgCl导致形成无溶剂的[（XA 2）Th（CH 2 Ph）2 ]（1）。随后1与1或2当量的B（C 6 F 5）3反应可分离出第一个非环戊二烯基act系元素烷基阳离子，[（XA 2）Th（CH 2 Ph）] [PhCH 2 B（C 6 F 5）3 ]（2），以及act系元素指示剂的稀有实例，[（XA 2）Th] [PhCH 2 B（C 6 F 5）3 ] 2（3）。指示剂的X射线晶体结构揭示了两个PhCH 2 B（C 6 F 5）3阴离子的π配位，并且溶液NMR光谱显示类似的接触离子配对模式在单阳离子中起作用。