[Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)((CH3)3SiCH2C(NCH(CH3)2)2)][B(C6F5)4] | 863221-71-0

• 英文名称: [Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)((CH3)3SiCH2C(NCH(CH3)2)2)][B(C6F5)4]
• 英文别名: [Ti(N-t-Bu)(Me3[9]aneN3)(Me3SiCH2C(N-i-Pr)2)][B(Ar(F))4]；[Ti(N(t)Bu)(Me3[9]aneN3)(Me3SiCH2C(N(i)Pr)2)][B(C6F5)4]
• CAS: 863221-71-0
• 化学式: C₂₄BF₂₀*C₂₄H₅₅N₆SiTi
• 分子量: 1182.75
• InChiKey: HPLOUUZXTFQZCK-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  [Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)(CH2Si(CH3)3)2] 、 三苯碳四(五氟苯基)硼酸盐 、 N,N'-二异丙基碳二亚胺 以 二氯甲烷 为溶剂， 以31%的产率得到[Ti(NC(CH3)3)(1,4,7-trimethyltriazacyclononane)((CH3)3SiCH2C(NCH(CH3)2)2)][B(C6F5)4]
  参考文献：
  名称：

  明确定义的亚胺基钛烷基阳离子：摩擦相互作用，迁移插入与[2 + 2]环加成反应以及任何过渡金属烷基阳离子的第一个结构鉴定的AlMe（3）加合物。

  摘要：

  亚胺基钛烷基阳离子[Ti（NtBu）（Me3 [9] aneN3）R] +（R = Me（3+）或CH2SiMe3（4+））具有很弱的α-原子或β-Si-C原子间的弱相互作用。分别根据13C和29Si NMR和DFT研究；（4+）与iPrNCNiPr的反应完全选择性地插入到Ti-烷基键中; 3+与AlMe3的反应生成了过渡金属烷基阳离子的第一个结构表征的AlMe3加合物（Me3 [9] aneN3 = 1,4,7-三甲基三氮杂环壬烷）。

  DOI：

  10.1039/b504567c

文献信息

• Ti═NR vs Ti−R′ Functional Group Selectivity in Titanium Imido Alkyl Cations from an Experimental Perspective
  作者：Paul D. Bolton、Marta Feliz、Andrew R. Cowley、Eric Clot、Philip Mountford

  DOI：10.1021/om800709f

  日期：2008.12.8

  A study of the reactions of the titanium imido methyl cation [Ti((NBu)-Bu-t)(Me-3[9]aneN(3))X](+) (5(+), X = Me) and key analogues (6(+), X = CH2SiMe3; 7(+), X = Cl) with a range of unsaturated substrates provides a comprehensive evaluation of reaction site selectivity in transition-metal cations which contain both Ti=NR and Ti-R ' functional groups as potential sites for 2 pi + 2 pi cycloaddition and migratory insertion, respectively. Cations 5+ and 6(+) reacted with MeCN to form Ti-R ' insertion products. Insertion reactions were also exclusively observed in their reactions with N,N '-disubstituted carbodiimides or tert-butyl isocyanate. In contrast, reaction of the chloride cation 7+ with diisopropylcarbodiimide or tert-butyl isocyanate afforded the unusual a adducts [Ti((NBu)-Bu-t)(Me-3[9]aneN(3))(L)Cl](+) (L = (PrNCNi)-Pr-i Pr, (BuNCO)-Bu-t), which slowly underwent 2,7 + 2 pi cycloaddition. Reaction of 5+ with the internal alkynes PhCCR (R = Ph, SiMe3) also showed exclusive preference for insertion into the Ti-Me bond. In contrast, reaction with terminal alkynes RCCH (R = Ph, SiMe3) yielded only the azametallacyclic products via 2-pi + 2 pi cycloaddition reactions. The chloride cation 7+ also underwent a 2 pi + 2 pi cycloaddition with PhCCH but was unreactive toward PhCCPh, ethylene, styrene, or 1-hexene.