[TiMe2(η5-C5Me4(CH2Ph))2] | 1169516-85-1

• 英文名称: [TiMe2(η5-C5Me4(CH2Ph))2]
• CAS: 1169516-85-1
• 化学式: C₃₄H₄₄Ti
• 分子量: 500.603
• InChiKey: SSRFCXSSBGKDFQ-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

• 作为反应物：
  描述：

  [TiMe2(η5-C5Me4(CH2Ph))2] 以 甲苯 为溶剂， 以95%的产率得到[TiMe(η5-C5Me4(CH2Ph))(η5:η1-C5Me4CH2-o-C6H4)]
  参考文献：
  名称：

  Thermolysis of titanocene methyl compounds bearing t-butyl- and benzyltetramethylcyclopentadienyl ligands

  摘要：

  Elimination of methane during thermolysis of title compounds results in the formation of sigma-Ti-C bond to t-butyl or benzyl group. The t-butyl-containing titanocene methyl compound [Ti(III)Me(eta(5)-C(5)Me(4)t-Bu)(2)] (5) eliminates methane at 110 degrees C to give cleanly [Ti(III)(eta(5):eta(1)-C5Me4CMe2CH2)(eta(5)-C(5)Me(4)t-Bu)] (6). The methyl derivative of analogous benzyl-containing titanocene [Ti(III)Me(eta(5)-C5Me4CH2Ph)(2)] was not isolated because it eliminated methane at ambient temperature to give [Ti(III)(eta(5):eta(1)-C5Me4CH2-o-C6H4)(eta(5)-C5Me4CH2Ph)] (7) with one phenyl ring linked to titanium atom in ortho-position. The corresponding titanocene dimethyl compound [TiMe2{eta(5)-C(5)Me(4)t-Bu)}(2)] (9) eliminates two methane molecules at 110 degrees C to give the singly tucked-in 1,1-dimethylethane-1,2-diyl-tethered titanocene [Ti{eta(5):eta(1):eta(1)-C5Me3(CH2)(CMe2CH2)}(eta(5)-C(5)Me(4)t-Bu)] (11). In distinction, the analogous benzyl derivative [TiMe2(eta(5)-C5Me4CH2Ph)(2)] (10) eliminates at 110 degrees C only one methane molecule to afford [TiMe(eta(5):eta(1)-C5Me4CH2-o-C6H4)(eta(5)-C5Me4CH2Ph)] (12) containing one phenyl group attached to titanium in o-position and one methyl group persisting on the titanium atom. This compound is stable at 150 degrees C for at least 3 h. The crystal structures of 5, 6, 7, and 10 were determined. (c) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.01.039
• 作为产物：
  描述：

  [TiCl2(η5-C5Me4(CH2Ph))2] 、 甲基锂 以 正己烷 为溶剂， 以81%的产率得到[TiMe2(η5-C5Me4(CH2Ph))2]
  参考文献：
  名称：

  Thermolysis of titanocene methyl compounds bearing t-butyl- and benzyltetramethylcyclopentadienyl ligands

  摘要：

  Elimination of methane during thermolysis of title compounds results in the formation of sigma-Ti-C bond to t-butyl or benzyl group. The t-butyl-containing titanocene methyl compound [Ti(III)Me(eta(5)-C(5)Me(4)t-Bu)(2)] (5) eliminates methane at 110 degrees C to give cleanly [Ti(III)(eta(5):eta(1)-C5Me4CMe2CH2)(eta(5)-C(5)Me(4)t-Bu)] (6). The methyl derivative of analogous benzyl-containing titanocene [Ti(III)Me(eta(5)-C5Me4CH2Ph)(2)] was not isolated because it eliminated methane at ambient temperature to give [Ti(III)(eta(5):eta(1)-C5Me4CH2-o-C6H4)(eta(5)-C5Me4CH2Ph)] (7) with one phenyl ring linked to titanium atom in ortho-position. The corresponding titanocene dimethyl compound [TiMe2{eta(5)-C(5)Me(4)t-Bu)}(2)] (9) eliminates two methane molecules at 110 degrees C to give the singly tucked-in 1,1-dimethylethane-1,2-diyl-tethered titanocene [Ti{eta(5):eta(1):eta(1)-C5Me3(CH2)(CMe2CH2)}(eta(5)-C(5)Me(4)t-Bu)] (11). In distinction, the analogous benzyl derivative [TiMe2(eta(5)-C5Me4CH2Ph)(2)] (10) eliminates at 110 degrees C only one methane molecule to afford [TiMe(eta(5):eta(1)-C5Me4CH2-o-C6H4)(eta(5)-C5Me4CH2Ph)] (12) containing one phenyl group attached to titanium in o-position and one methyl group persisting on the titanium atom. This compound is stable at 150 degrees C for at least 3 h. The crystal structures of 5, 6, 7, and 10 were determined. (c) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.01.039