[(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2]*toluene | 927674-74-6

• 分子结构分类: 有机化合物
• 英文名称: [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2]*toluene
• 英文别名: [2,7-ditert-butyl-5-[2,6-di(propan-2-yl)phenyl]azanidyl-9,9-dimethylxanthen-4-yl]-[2,6-di(propan-2-yl)phenyl]azanide;methanidyl(trimethyl)silane;thorium(4+);toluene
• CAS: 927674-74-6
• 化学式: C₇H₈*C₅₅H₈₄N₂OSi₂Th
• 分子量: 1169.63
• InChiKey: CCVBBLCOBZZYAB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  21.27
• 重原子数：
  68
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  11.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene 以 甲苯 为溶剂， 生成 [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2]*toluene
  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