[σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti[η3-S2CNMe2] | 937725-24-1

• 英文名称: [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti[η3-S2CNMe2]
• CAS: 937725-24-1
• 化学式: C₉H₂₅B₉N₂OS₂Ti
• 分子量: 386.621
• InChiKey: GJLAFMPSILALBI-UHFFFAOYSA-M

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：

  二硫化碳 、 [ς:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti-(NMe2) 以 not given 为溶剂， 生成 [σ:η1:η5-(OCH2)(Me2NCH2)C2B9H9]Ti[η3-S2CNMe2]
  参考文献：
  名称：

  Titanacarborane mediated C–N bond forming/breaking reactions

  摘要：

  Constrained-geometry titanacarboranes [sigma: eta(1):eta(5)-(OCH2)(R2NCH2)C2B9H9]Ti(NR2) (R = Me, Et) are synthesized via an unexpected reaction of [Me3NH][mu-7,8-CH2OCH2-7,8-C2B9H10] with Ti(NR2)(4) (R = Me, Et), involving a C-O bond cleavage and C-N bond formation. These complexes can be readily converted to new amide species or alkoxide by reacting with amines or esters, respectively. Insertion of a series of unsaturated molecules into the Ti-N bond of the aforementioned complexes results in the formation of various half-sandwich titanacarboranes. [sigma: eta(1): eta(5)-(OCH2)(Me2NCH2)C2B9H9]Ti(NMe2) is also able to efficiently catalyze the hydroamination of carbodiimides and the transamination of guanidines. These results are summarized in this brief account. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.11.010

文献信息

• Synthesis, Structure, and Reactivity of [σ:η¹:η⁵-(OCH₂)(Me₂NCH₂)C₂B₉H₉]Ti(NR₂) (R = Me, Et)
  作者：Hao Shen、Hoi-Shan Chan、Zuowei Xie

  DOI：10.1021/om070128q

  日期：2007.5.1

  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.