bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)titanium dichloride | 455317-60-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)titanium dichloride
• 英文别名: 2,2,5,5-Tetramethyl-1-azanida-2,5-disilacyclopentane;titanium(4+);dichloride；2,2,5,5-tetramethyl-1-azanida-2,5-disilacyclopentane;titanium(4+);dichloride
• CAS: 455317-60-9
• 化学式: C₁₂H₃₂Cl₂N₂Si₄Ti
• 分子量: 435.527
• InChiKey: NPIRRGJWWCVCLL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -0.43
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)titanium dichloride 、 丙基锂 以 氘代苯 为溶剂， 生成 di(propyn-1-yl)bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)titanium
  参考文献：
  名称：

  Novel titana-2,4-cyclopentadienes by 1,1-alkylboration

  摘要：

  Bis(trimethylsilyl)amino-(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)-titanium dichloride (3) and bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)-titanium dichloride (4) were prepared and converted into the di(1-alkynyl)titanium derivatives, (Me3Si)(2)N[(CH2Me2Si)(2)N]Ti(Cequivalent toC-R)(2) (5) and [(CH2Me2Si)(2)N](2)Ti(Cequivalent toC-R)(2) (6) [R = Me (a), Ph (b), SiMe3 (c)]. The reaction of 5a and 5b with trialkylboranes such as Et,B leads almost quantitatively to titana-2,4-cyclopentadienes 7a and 7b, in which a diethylboryl group functions as a substituent in 3-position. In the same manner, 6b reacts with Et3B or Pr3B to titana-2,4-cyclopentadienes 8b or 9b, respectively. It is proposed that these reactions proceed by 1,1-alkylboration. Compound 5c also reacts with Et3B, however, a complex mixture was obtained. All products were characterised by H-1-, B-11-, C-13-, N-15- and Si-29-NMR spectroscopy. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01135-x
• 作为产物：
  描述：

  2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopenta-1-yl-titanium trichloride 、 1-lithio-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane 以 正己烷 为溶剂， 以95%的产率得到bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)titanium dichloride
  参考文献：
  名称：

  Novel titana-2,4-cyclopentadienes by 1,1-alkylboration

  摘要：

  Bis(trimethylsilyl)amino-(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)-titanium dichloride (3) and bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)-titanium dichloride (4) were prepared and converted into the di(1-alkynyl)titanium derivatives, (Me3Si)(2)N[(CH2Me2Si)(2)N]Ti(Cequivalent toC-R)(2) (5) and [(CH2Me2Si)(2)N](2)Ti(Cequivalent toC-R)(2) (6) [R = Me (a), Ph (b), SiMe3 (c)]. The reaction of 5a and 5b with trialkylboranes such as Et,B leads almost quantitatively to titana-2,4-cyclopentadienes 7a and 7b, in which a diethylboryl group functions as a substituent in 3-position. In the same manner, 6b reacts with Et3B or Pr3B to titana-2,4-cyclopentadienes 8b or 9b, respectively. It is proposed that these reactions proceed by 1,1-alkylboration. Compound 5c also reacts with Et3B, however, a complex mixture was obtained. All products were characterised by H-1-, B-11-, C-13-, N-15- and Si-29-NMR spectroscopy. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01135-x

文献信息

• N‐Silylaminotitanium Chlorides — Synthesis, Structures, Multinuclear Magnetic Resonance, and some Applications
  作者：Bernd Wrackmeyer、Jürgen Weidinger、Andreas Pedall、Wolfgang Milius

  DOI：10.1002/zaac.200390147

  日期：2003.5

  N‐Silylaminotitanium trichlorides, Me₃S(R)N‐TiCl₃ (18) [R = ^tBu (a), SiMe₃ (b), 9‐borabicyclo[3.3.1]nonyl (9‐BBN)(c)], and (CH₂SiMe₂)₂N‐TiCl₃ (18d) were obtained in high yield and high purity from the reaction of the respective bis(silylamino)plumbylene with an excess of titanium tetrachloride. The crystal structure of 18a was determined by X‐ray analysis. The reactions of the analogous stannylenes with an excess of TiCl₄ did not lead to 18. N‐Lithio‐trimethylsilyl[9‐(9‐borabicyclo[3.3.1]nonyl)]amine (8) was prepared, structurally characterized and used for the synthesis of a new bis(amino)stannylene 10 and a plumbylene 11. The compounds 18a—d served as ideal starting materials for the synthesis of bis(silylamino)titanium dichlorides, where the silylamino groups can be identical (19) or different (20). This was achieved either by the reaction of 18 again with bis(amino)plumbylenes or with lithium N‐silylamides. In contrast to the direct synthesis starting from titanium tetrachloride and two equivalents of the respective lithium amide, which in general affords 19 with identical amino groups only in low yield, the procedure starting from 18 is much more versatile and gave the pure compounds 19 or 20 in almost quantitative yield. Further treatment of the dichlorides 19 or 20 with lithium amides led to tris(amino)titanium chlorides 21. The dichlorides 19 or 20 reacted with two equivalents of alkynyllithium reagents to give the first well characterized examples of di(alkyn‐1‐yl)bis(N‐silylamino)titanium compounds 22—27. These compounds reacted with trialkylboranes (triethyl or tripropylborane) by 1, 1‐organoboration. In some cases, the extremely reactive reaction products could be identified as novel 1, 1‐bis(silylamino)titana‐2, 4‐cyclopentadienes 28—31 bearing a dialkylboryl group in 3‐position. In solution, the proposed structures of all products were deduced from a consistent set of data derived from multinuclear magnetic resonance spectroscopy (¹H, ¹¹B, ¹³C, ¹⁴N, ¹⁵N, ²⁹Si, ³⁵Cl NMR).

  摘要 从各自的双(硅氨)铅烯与过量的四氯化钛的反应中，以高产率和高纯度获得了 N-硅氨钛三氯化物 Me3S(R)N-TiCl3 (18) [R = tBu (a), SiMe3 (b), 9-borabicyclo[3.3.1]nonyl (9-BBN)(c)] 和 (CH2SiMe2)2N-TiCl3 (18d)。通过 X 射线分析确定了 18a 的晶体结构。类似的锡烯与过量的 TiCl4 反应并没有生成 18a。制备了 N-硫代-三甲基硅烷基[9-(9-硼杂双环[3.3.1]壬基)]胺 (8)，对其进行了结构表征，并用于合成新的双(氨基)锡烯 10 和铅烯 11。化合物 18a-d 是合成双（硅烷基氨基）二氯化钛的理想起始原料，其中的硅烷基氨基可以是相同的（19）或不同的（20）。这可以通过 18 与双（氨基）plumbylenes 或 N-硅烷基锂反应来实现。与从四氯化钛和两个当量的相应锂酰胺开始的直接合成法相比，从 18 开始的程序用途更广，几乎可以定量得到纯化合物 19 或 20。用锂酰胺进一步处理二氯化物 19 或 20，可得到三（氨基）钛氯化物 21。二氯化物 19 或 20 与两个当量的炔锂试剂反应后，得到了首批特征明确的二(炔-1-基)双(N-硅烷基氨基)钛化合物 22-27。这些化合物与三烷基硼烷（三乙基或三丙基硼烷）发生 1，1-有机还原反应。在某些情况下，反应极为剧烈的反应产物可被鉴定为在 3 位带有二烷基硼烷基团的新型 1，1-双（硅烷基氨基）钛-2，4-环戊二烯 28-31。在溶液中，通过多核磁共振光谱（1H、11B、13C、14N、15N、29Si、35Cl NMR）获得的一组一致数据推断出了所有产物的拟议结构。
• Novel titana-2,4-cyclopentadienes by 1,1-alkylboration
  作者：Bernd Wrackmeyer、Andreas Pedall、Jürgen Weidinger

  DOI：10.1016/s0022-328x(02)01135-x

  日期：2002.4

  Bis(trimethylsilyl)amino-(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)-titanium dichloride (3) and bis(2,2,5,5-tetramethyl-1,2,5-azadisila-cyclopent-1-yl)-titanium dichloride (4) were prepared and converted into the di(1-alkynyl)titanium derivatives, (Me3Si)(2)N[(CH2Me2Si)(2)N]Ti(Cequivalent toC-R)(2) (5) and [(CH2Me2Si)(2)N](2)Ti(Cequivalent toC-R)(2) (6) [R = Me (a), Ph (b), SiMe3 (c)]. The reaction of 5a and 5b with trialkylboranes such as Et,B leads almost quantitatively to titana-2,4-cyclopentadienes 7a and 7b, in which a diethylboryl group functions as a substituent in 3-position. In the same manner, 6b reacts with Et3B or Pr3B to titana-2,4-cyclopentadienes 8b or 9b, respectively. It is proposed that these reactions proceed by 1,1-alkylboration. Compound 5c also reacts with Et3B, however, a complex mixture was obtained. All products were characterised by H-1-, B-11-, C-13-, N-15- and Si-29-NMR spectroscopy. (C) 2002 Elsevier Science B.V. All rights reserved.