[(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)(η6-C6H6)][B(C6F5)4]*C6H6 | 1133953-67-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮
• 英文名称: [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)(η6-C6H6)][B(C6F5)4]*C6H6
• 英文别名: benzene;[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;tetrakis(2,3,4,5,6-pentafluorophenyl)boranuide;thorium(4+)
• CAS: 1133953-67-9
• 化学式: C₆H₆*C₂₄BF₂₀*C₅₇H₇₉N₂OSiTh
• 分子量: 1825.55
• InChiKey: BPERUIWQKPDFHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  26.8
• 重原子数：
  113
• 可旋转键数：
  12
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  11.2
• 氢给体数：
  0
• 氢受体数：
  25

反应信息

• 作为反应物：
  描述：

  [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)(η6-C6H6)][B(C6F5)4]*C6H6 、 三甲基膦 以 not given 为溶剂， 生成 [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)(PMe3)(x)][B(C6F5)4]
  参考文献：
  名称：

  Cationic Thorium Alkyl Complexes of Rigid NON- and NNN-Donor Ligands: π-Arene Coordination as a Persistent Structural Motif

  摘要：

  Reaction of the neutral dialkyl complex [(XA(2))Th(CH2SiMe3)(2)] {1; XA(2) = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene} with [CPh3][B(C6F5)(4)] in benzene or toluene at room temperature resulted in the formation of [(XA(2))Th(CH2SiMe3)(eta(6)-arene)][B(C6F5)(4)] {arene = C6H6 (5) and toluene (5B)}, which were characterized by H-1, C-13, and 2D NMR spectroscopy and by X-ray crystallography (for 5). In close analogy, reaction of [(XA(2))Th(CH2Ph)(2)] (3) with [CPh3][B(C6F5)(4)] in toluene at room temperature resulted in the formation of 1 equiv of Ph3CCH2R (R = Ph) and precipitation of an insoluble orange-brown oil, which upon layering with hexanes yielded crystals of [(XA(2))Th(eta(2)-CH2Ph)(eta(6)- C6H5Me)][B(C6F5)(4)] (6). NMR investigation of the reactions of 1 and 3 with substoichiometric amounts of [CPh3][B(C6F5)(4)] provided no evidence for dinuclear monocation formation. By contrast, reaction of [(BDPP)Th(CH2Ph)(2)] {4; BDPP = 2,6-bis(2,6-diisopropylanilidomethyl)pyridine) with 0.5 equiv of [CPh3][B(C6F5)(4)] resulted in the precipitation of an insoluble oil containing a mixture of a mononuclear and a dinuclear cation; the dinuclear cation was identified as [(BDPP)Th(eta(2)-CH2Ph)(mu-eta(1): eta(6)-CH2Ph)Th(eta(1)-CH2Ph)(BDPP)[B(C6F5)(4)] (7) by X-ray crystallography. Reaction of complex 3 with B(C6F5)(3) resulted in the formation of [(XA(2))Th(eta(1)-CH2Ph)] [eta(6)-PhCH2B(C6F5)(3)] (9), which was characterized in solution by NMR spectroscopy. Complexes 5, 5B, and 6 are rare examples of arene solvent-separated ion pairs, complex 9 exists as a tight contact ion pair, and dinuclear 7 exhibits a unique benzyl ligand bridging mode. The structures of cations 5-7 and 9 highlight a pronounced tendency for these systems to engage in arene pi-coordination.

  DOI：

  10.1021/om800624t
• 作为产物：
  描述：

  [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2] 、 三苯碳四(五氟苯基)硼酸盐 、 苯 以 苯 为溶剂， 生成 [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)(η6-C6H6)][B(C6F5)4]*C6H6
  参考文献：
  名称：

  Cationic Thorium Alkyl Complexes of Rigid NON- and NNN-Donor Ligands: π-Arene Coordination as a Persistent Structural Motif

  摘要：

  Reaction of the neutral dialkyl complex [(XA(2))Th(CH2SiMe3)(2)] {1; XA(2) = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene} with [CPh3][B(C6F5)(4)] in benzene or toluene at room temperature resulted in the formation of [(XA(2))Th(CH2SiMe3)(eta(6)-arene)][B(C6F5)(4)] {arene = C6H6 (5) and toluene (5B)}, which were characterized by H-1, C-13, and 2D NMR spectroscopy and by X-ray crystallography (for 5). In close analogy, reaction of [(XA(2))Th(CH2Ph)(2)] (3) with [CPh3][B(C6F5)(4)] in toluene at room temperature resulted in the formation of 1 equiv of Ph3CCH2R (R = Ph) and precipitation of an insoluble orange-brown oil, which upon layering with hexanes yielded crystals of [(XA(2))Th(eta(2)-CH2Ph)(eta(6)- C6H5Me)][B(C6F5)(4)] (6). NMR investigation of the reactions of 1 and 3 with substoichiometric amounts of [CPh3][B(C6F5)(4)] provided no evidence for dinuclear monocation formation. By contrast, reaction of [(BDPP)Th(CH2Ph)(2)] {4; BDPP = 2,6-bis(2,6-diisopropylanilidomethyl)pyridine) with 0.5 equiv of [CPh3][B(C6F5)(4)] resulted in the precipitation of an insoluble oil containing a mixture of a mononuclear and a dinuclear cation; the dinuclear cation was identified as [(BDPP)Th(eta(2)-CH2Ph)(mu-eta(1): eta(6)-CH2Ph)Th(eta(1)-CH2Ph)(BDPP)[B(C6F5)(4)] (7) by X-ray crystallography. Reaction of complex 3 with B(C6F5)(3) resulted in the formation of [(XA(2))Th(eta(1)-CH2Ph)] [eta(6)-PhCH2B(C6F5)(3)] (9), which was characterized in solution by NMR spectroscopy. Complexes 5, 5B, and 6 are rare examples of arene solvent-separated ion pairs, complex 9 exists as a tight contact ion pair, and dinuclear 7 exhibits a unique benzyl ligand bridging mode. The structures of cations 5-7 and 9 highlight a pronounced tendency for these systems to engage in arene pi-coordination.

  DOI：

  10.1021/om800624t