(2,6-(CHMe2)2C6H3NC(tBu)CHC(tBu)NC6H3(CHMe2)2-2,6)ZrCl3 | 827342-27-8

• 英文名称: (2,6-(CHMe2)2C6H3NC(tBu)CHC(tBu)NC6H3(CHMe2)2-2,6)ZrCl3
• CAS: 827342-27-8
• 化学式: C₃₅H₅₃Cl₃N₂Zr
• 分子量: 699.402
• InChiKey: PPRNXIADQVVTPP-IYVJWHKNSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (2,6-(CHMe2)2C6H3NC(tBu)CHC(tBu)NC6H3(CHMe2)2-2,6)ZrCl3 以 乙醚 为溶剂， 生成 (2,6-(CHMe2)2C6H3NC(tBu)CHC(tBu)NC6H3(CHMe2)2-2,6)Zr(CH2SiMe3)2Cl*OEt2
  参考文献：
  名称：

  Terminal Zirconium Imides Prepared by Reductive C−N Bond Cleavage

  摘要：

  Toluene reflux of ZrCl4 with Li(Nacnac) (Nacnac(-) = [Ar]NC(tBu)CHC(tBu)N[Ar], Ar = 2,6-[CH(CH3)(2)](2)C6H3) provides the complex (Nacnac)ZrCl3 in 75% yield. Cl- substitution for OTf- is readily achieved with 3 equiv of AgOTf to yield 77% of the complex (Nacnac)Zr(OTf)(2)(eta(2)-OTf). The coordination mode of the three triflato groups was determined by a combination of single-crystal X-ray analysis and F-19 COSY experiments. Addition of 2 equiv of LiCH2XMe3 (X = C, Si) to (Nacnac)ZrCl4 in Et2O affords the bis(alkyl) systems (Nacnac)Zr(CH2XMe3)(2)Cl in good yield (X = C, 86%; X = Si, 91%). In contrast, reaction of (Nacnac)Zr(OTf)(2)(eta(2)-OTf) with 2 equiv of LiCH2CMe3 leads instead to formation of the terminal zirconium-imido complex [(NactBu)Zr=NAr(mu(2)-OTf)](2) (NactBu(-) = [2,6-(CHMe2)(2)C6H3]NC(tBu)CHC(tBu)). Likewise, reduction of (Nacnac)ZrCl3 with 2 equiv of KC8 in THF also affords a terminal zirconium-imido species, (NactBu)Zr=NAr(Cl)(THF). The zirconium-imido compounds described herein result from reductive cleavage of the C-N bond of the imine functionality contained in the Nacnac(-) ligand. The complexes (Nacnac)ZrCl3, (Nacnac)Zr(OTf)(2)(eta(2)-OTf), (Nacnac)Zr(CH2XMe3)(2)Cl, [(NactBu)Zr=NAr(mu(2)-OTf)](2), and (NactBu)Zr=NAr(Cl)(THF) have been fully characterized, and a single-crystal X-ray diffraction analysis is reported for each.

  DOI：

  10.1021/om049332t
• 作为产物：
  描述：

  Li[((C6H3(CH(CH3)2)2-2,6)NC(t-Bu)CHC(t-Bu)N(C6H3(CH(CH3)2)2-2,6)] 、 氯化锆(IV) 以 甲苯 为溶剂， 以75%的产率得到(2,6-(CHMe2)2C6H3NC(tBu)CHC(tBu)NC6H3(CHMe2)2-2,6)ZrCl3
  参考文献：
  名称：

  Terminal Zirconium Imides Prepared by Reductive C−N Bond Cleavage

  摘要：

  Toluene reflux of ZrCl4 with Li(Nacnac) (Nacnac(-) = [Ar]NC(tBu)CHC(tBu)N[Ar], Ar = 2,6-[CH(CH3)(2)](2)C6H3) provides the complex (Nacnac)ZrCl3 in 75% yield. Cl- substitution for OTf- is readily achieved with 3 equiv of AgOTf to yield 77% of the complex (Nacnac)Zr(OTf)(2)(eta(2)-OTf). The coordination mode of the three triflato groups was determined by a combination of single-crystal X-ray analysis and F-19 COSY experiments. Addition of 2 equiv of LiCH2XMe3 (X = C, Si) to (Nacnac)ZrCl4 in Et2O affords the bis(alkyl) systems (Nacnac)Zr(CH2XMe3)(2)Cl in good yield (X = C, 86%; X = Si, 91%). In contrast, reaction of (Nacnac)Zr(OTf)(2)(eta(2)-OTf) with 2 equiv of LiCH2CMe3 leads instead to formation of the terminal zirconium-imido complex [(NactBu)Zr=NAr(mu(2)-OTf)](2) (NactBu(-) = [2,6-(CHMe2)(2)C6H3]NC(tBu)CHC(tBu)). Likewise, reduction of (Nacnac)ZrCl3 with 2 equiv of KC8 in THF also affords a terminal zirconium-imido species, (NactBu)Zr=NAr(Cl)(THF). The zirconium-imido compounds described herein result from reductive cleavage of the C-N bond of the imine functionality contained in the Nacnac(-) ligand. The complexes (Nacnac)ZrCl3, (Nacnac)Zr(OTf)(2)(eta(2)-OTf), (Nacnac)Zr(CH2XMe3)(2)Cl, [(NactBu)Zr=NAr(mu(2)-OTf)](2), and (NactBu)Zr=NAr(Cl)(THF) have been fully characterized, and a single-crystal X-ray diffraction analysis is reported for each.

  DOI：

  10.1021/om049332t