[(2,6-bis(2,6-diisopropylanilidomethyl)pyridine)ThCl2(dme)] | 927674-68-8

• 英文名称: [(2,6-bis(2,6-diisopropylanilidomethyl)pyridine)ThCl2(dme)]
• CAS: 927674-68-8
• 化学式: C₃₅H₅₁Cl₂N₃O₂Th
• 分子量: 848.753
• InChiKey: AMGMPTKRYOSBIG-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：

  [(2,6-bis(2,6-diisopropylanilidomethyl)pyridine)ThCl2(dme)] 、 甲苯 以 正己烷 、 甲苯 为溶剂， 生成 [(2,6-bis(2,6-diisopropylanilidomethyl)pyridine)ThCl2(dme)]*2toluene
  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
• 作为产物：
  描述：

  ThCl₄(DME)₂ 、 2,6-bis((2,6-diisopropylphenyl)aminomethyl)pyridine 在 LiCH₂SiMe₃ 作用下， 以 甲苯 为溶剂， 以85%的产率得到[(2,6-bis(2,6-diisopropylanilidomethyl)pyridine)ThCl2(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

• A thermally robust di-n-butyl thorium complex with an unstable dimethyl analogue
  作者：Carlos A. Cruz、David J. H. Emslie、Hilary A. Jenkins、James F. Britten

  DOI：10.1039/c002122a

  日期：——

  Methyl and n-butyl thorium complexes of a rigid 2,6-bis(anilidomethyl)pyridine ligand have been prepared; the n-butyl complex is thermally stable, even at 60 °C, while the methyl complexes exhibit a high tendency to eliminate methane viaσ-bond metathesis.