(C5Me5)2Ti[(η(1)-C.tplbond.CSiMe3)2] | 176094-82-9

• 分子结构分类: 有机化合物
• 英文名称: (C5Me5)2Ti[(η(1)-C.tplbond.CSiMe3)2]
• 英文别名: ethynyl(trimethyl)silane;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;titanium(4+)
• CAS: 176094-82-9
• 化学式: C₃₀H₄₈Si₂Ti
• 分子量: 512.762
• InChiKey: YNRXHLJSXCFHHZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  (C5Me5)2Ti(η(2)-bis(trimethylsilyl)acetylene) 、 三甲基乙炔基硅 以 正己烷 为溶剂， 生成 (C5Me5)2Ti[(η(1)-C.tplbond.CSiMe3)2]
  参考文献：
  名称：

  Permethyltitanocene-bis(trimethylsilyl) acetylene, an efficient catalyst for the head-to-tail dimerization of 1-alkynes

  摘要：

  In the series of the (C(5)H(5-n)Me(n))(2)Ti[eta(2)-C-2(SiMe(3))(2)] (n=0-5) (1A-1F) complexes only (C(5)Me(5))(2)Ti[eta(2)-C-2(SiMe(3))(2)] (1F) catalyzed the linear head-to-tail dimerization of 1-alkynes. A selectivity of better than 98% and a turnover number (TN) in the range 1200-1500 mmol of 1-alkyne per mmol of Ti was obtained after 14 d at 30 degrees C for 1-pentyne, 1-hexyne, cyclohexylethyne, phenylethyne and trimethylsilylethyne. Among other complexes in the series, 1A-1D attained TN less than or equal to 25 after 5 d at 30 degrees C and produced mainly a mixture of 1,3,5- and 1,2,4-trisubstituted benzene derivatives. The complex (C(5)HMe(4))(2)Ti[eta(2)-C-2(SiMe(3))(2)] (1E) afforded ca. 20% of the head-to-tail dimers in addition to cyclotrimers but its activity was extremely low, corresponding to TN similar to 7. The rate of dimerization by 1F is controlled by the slow exchange rate of 1-alkynes with bis(trimethylsilyl)acetylene.

  DOI：

  10.1016/0022-328x(95)05806-z

文献信息

• Redox-Disproportionation of a Decamethyltitanocene(III) Isonitrile Alkynyl Complex
  作者：Fabian Reiß、Kai Altenburger、Dirk Hollmann、Anke Spannenberg、Haijun Jiao、Perdita Arndt、Uwe Rosenthal、Torsten Beweries

  DOI：10.1002/chem.201701374

  日期：2017.6.12

  A mixed decamethyltitanocene(III) isonitrile alkynyl complex (7) was synthesized by the sequential introduction of the isonitrile and alkynyl ligands. Direct synthesis results in the formation of the diamagnetic decamethyltitanocene bis(isonitrile) (2) and bis(alkynyl) (3) complexes. Compound 7 undergoes disproportionation at room temperature to give 2 and 3. All complexes were fully characterized

  通过顺序引入异腈和炔基配体，合成了混合的十甲基噻吩并茂（III）异腈炔基配合物（7）。直接合成导致反磁性十甲基钛并茂双（腈）（2）和双（炔基）（3）配合物的形成。化合物7在室温下歧化，得到2和3。所有复合物均通过IR，NMR和EPR光谱以及质谱进行了充分表征。报道了配合物2和7的分子结构。这些配合物的稳定性和反应性通过DFT计算得以合理化。