[(σ:η1:η5-(OCH2)(Et2NCH2)C2B9H9)Ti(OMe)]2 | 937725-31-0

• 英文名称: [(σ:η1:η5-(OCH2)(Et2NCH2)C2B9H9)Ti(OMe)]2
• CAS: 937725-31-0
• 化学式: C₁₈H₅₂B₁₈N₂O₄Ti₂
• 分子量: 650.98
• InChiKey: ROCXUIJLMWQCEX-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

• 作为产物：
  描述：

  [σ:η1:η5-(OCH2)(Et2NCH2)C2B9H9]Ti(NEt2) 、 丁炔二酸二甲酯 以 甲苯 为溶剂， 生成 [(σ:η1:η5-(OCH2)(Et2NCH2)C2B9H9)Ti(OMe)]2
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)

  摘要：

  Interaction of [Me3NH][7,8-CH2OCH2-7,8-C2B9H10] with M(NR2)(4) gave the simple amine elimination products [eta(5)-(CH2OCH2)C2B9H9]M(NMe2)(2)(NHMe2) (M = Zr (2a), Hf (2b)) or the unexpected C-O bond cleavage products [sigma:eta(1):eta(5)-(OCH2)(Me2NCH2)C2B9H9]Ti(NR2) (R = Me (3a), Et (3b)). The higher oxophilicity of the Ti center provides the driving force for the latter reactions. It is suggested that the C-O bond cleavage is prior to the amine elimination in the formation of 3a,b. This serves as a convenient and practical method for the preparation of constrained-geometry half-sandwich metallacarboranes with two different functional sidearms. Complex 3a can undergo a clean amine exchange reaction to produce new constrained-geometry titanacarborane amides. Reactions of 3a with unsaturated molecules CyNCNCy, SCS, Xyl-NC, PhCN, (BuNCS)-N-n, Ph2CCO, and PhNCO gave monoinsertion products. They, except for [sigma:eta(1):eta(5)-(OCH2)(Me2NCH2)C2B9H9]Ti[eta(3)-CyNC(NMe2)NCy] (7), do not react with amines. In sharp contrast, 7 can react readily with Me2NH to regenerate 3a and release guanidine, which leads to the discovery of new catalytic guanylation of amines. All new complexes were fully characterized by various spectroscopic techniques and elemental analyses. Most of them were further confirmed by single-crystal X-ray analyses.

  DOI：

  10.1021/om070128q