[(CpTiCl(NP-t-Bu3)(CH2CH2))2SiCl2] | 912363-85-0

• 英文名称: [(CpTiCl(NP-t-Bu3)(CH2CH2))2SiCl2]
• CAS: 912363-85-0
• 化学式: C₃₈H₇₂Cl₄N₂P₂SiTi₂
• 分子量: 884.608
• InChiKey: VZSLFGWVWYZRIM-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

• 作为产物：
  描述：

  四氯化硅 、 [CpTiCl(NP-t-Bu3)(C4H8)] 在 PMe₃ 作用下， 以 正戊烷 为溶剂， 以78%的产率得到[(CpTiCl(NP-t-Bu3)(CH2CH2))2SiCl2]
  参考文献：
  名称：

  Functionalizing Titanium−Phosphinimide Complexes

  摘要：

  The reaction of the titanacycle CpTi(NPt-Bu-3)(C4H8)(1) with benzyl halides, 4-bromo-1-butene, and allyl chloride proceeds with loss of ethylene to give CpTiX(NPt-Bu-3)(CH2Ph) (X = Cl, 3; Br, 4), CpTiBr-(NPt-Bu-3)(CH2CH2CHCH2) (5), and CpTiCl(NPt-Bu-3)(CH2CHCH2) (6), respectively. Complexes 4 and 6 were readily alkylated to CpTiMe(NPt-Bu-3)(CH2Ph) (7) and CpTiMe(NPt-Bu-3)(CH2CHCH2) (8), respectively. Loss of ethylene also occurs on reaction of 1 with bipyridine to give CpTi(NPt-Bu-3)(bipy) (9). In contrast, reaction of 1 with ClSiMePh2 in the presence of PMe3 gave CpTiCl(NPt-Bu-3)(CH2CH2SiPh2Me) (10). In a similar fashion, the two-carbon derivatives CpTiCl(NPt-Bu-3)(CH2CH2SiMe3) (11), CpTiCl(NPt-Bu-3)(CH2CH2Si(SiMe3)(3)) (12), CpTi(NPt-Bu-3)(CH2CH2SiMe3)(OSO2CF3) (13), CpTiCl(NPt-Bu-3)(CH(2)CH(2)Snn-Bu-3) (14), CpTiCl(NPt-Bu-3)(CH2CH2SiCl3) (15), and [CpTiCl(NPt-Bu-3)(CH2CH2)](2)-SiCl2 (16) were produced. In the absence of PMe3, reaction of 1 with SiCl4 and ClSnMe3 gave the four-carbon derivatives CpTiCl(NPt-Bu-3)(CH2CH2CH2CH2SiCl3) (17) and CpTiCl(NPt-Bu-3)(CH2CH2CH2CH2SnMe3) (18), while reaction of 1 with ClSnPh3 gave only the two-carbon chain derivative CpTiCl(NPtBu3)(CH2CH2SnPh3) (19). Nonetheless, in the presence and absence of PMe3 reaction of 1 with ClBcat or ClPPh2 gave the analogous two- and four-carbon derivatives CpTiCl(NPt-Bu-3)(CH(2)CH(2)Bcat) (20), CpTiCl(NPt-Bu-3)(CH(2)CH(2)CH(2)CH(2)Bcat) (21), CpTiCl(NPt-Bu-3)(CH2CH2PPh2)(22), and CpTiCl(NPtBu3)(CH2CH2CH2CH2PPh2) (23), respectively. The corresponding species CpTiCl(NPt-Bu-3)(CH2CHCH3)CH(CH3)CH2PPh2) (24) was prepared from CpTi(NPt-Bu-3)(CH2CHMe)(2) (2), while complexation of 23 and 24 afforded CpTiCl(NPt-Bu-3)(CH2CH2CH2CH2PPh2)RhCl(cod) (25) and CpTiCl(NPt-Bu-3)(CH2CH(CH3)CH(CH3)CH2PPh2)RhCl(cod) (26). The mechanisms affording the functionalized two- and four-carbon derivatives above are discussed and the implications considered.

  DOI：

  10.1021/om060565p