[(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2] | 927674-71-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2]
• CAS: 927674-71-3
• 化学式: C₅₅H₈₄N₂OSi₂Th
• 分子量: 1077.49
• InChiKey: ONCVQRKVMOKSTP-UHFFFAOYSA-N

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：

  [(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 以 氟苯 为溶剂， 生成
  参考文献：
  名称：

  铀 (IV) 烷基阳离子：合成、结构、与钍 (IV) 类似物的比较，以及芳烃配位对热稳定性和乙烯聚合活性的影响

  摘要：

  [(XA 2 )U(CH 2 SiMe 3 ) 2 ] ( 1 ; XA 2 = 4,5-bis(2,6-diisopropylanilido)-2,7-di- tert -butyl-9,9-dimethylxanthene 的反应) 与 1 当量的 [Ph 3 C][B(C 6 F 5 ) 4 ] 在芳烃溶剂中得到芳烃配位的铀烷基阳离子，[(XA 2 )U(CH 2 SiMe 3 )(η n -arene) ][B(C 6 F 5 ) 4 ] {芳烃 = 苯 ( 2 ), 甲苯 ( 3 ), 溴苯 ( 4) 和氟苯 ( 5 )}。化合物2、3和5进行了晶体学表征，并且在所有情况下，芳烃都是 π 配位的。2-5的溶液 NMR 研究表明 [(XA 2 )U(CH 2 SiMe 3 )] +阳离子的结合偏好遵循以下顺序：甲苯 ≈ 苯 > 溴苯 > 氟苯。在 C 6 H 5 R（分别为 R =

  DOI：

  10.1039/d2sc04302e
• 作为产物：
  描述：

  trimethylsilylmethyllithium 、 [(XA2)2ThCl2(dme)] 以 甲苯 为溶剂， 以65%的产率得到[(4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene)Th(CH2SiMe3)2]
  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

• Cationic Thorium Alkyl Complexes of Rigid NON- and NNN-Donor Ligands: π-Arene Coordination as a Persistent Structural Motif
  作者：Carlos A. Cruz、David J. H. Emslie、Craig M. Robertson、Laura E. Harrington、Hilary A. Jenkins、James F. Britten

  DOI：10.1021/om800624t

  日期：2009.3.23

  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.