[TiCl2(η5-C5Me4(CH2Ph))2] | 238421-84-6

• 英文名称: [TiCl2(η5-C5Me4(CH2Ph))2]
• CAS: 238421-84-6
• 化学式: C₃₂H₃₈Cl₂Ti
• 分子量: 541.44
• InChiKey: ZXKJKHGSQCCXPX-UHFFFAOYSA-L

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

• 作为反应物：
  描述：

  [TiCl2(η5-C5Me4(CH2Ph))2] 在 Mg 作用下， 以 四氢呋喃 为溶剂， 生成 [TiCl(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

文献信息

• Photoinduced Generation of Catalytic Complexes from Substituted-Titanocene−Bis(trimethylsilyl)ethyne Complexes: Contribution to the Mechanism of the Catalytic Head-to-Tail Dimerization of Terminal Alkynes
  作者：Petr Štěpnička、Róbert Gyepes、Ivana Císařová、Michal Horáček、Jiří Kubišta、Karel Mach

  DOI：10.1021/om9905714

  日期：1999.11.1

  that do not react further with an excess of tert-butylethyne and (trimethylsilyl)ethyne in the dark, B type complexes induce rapid dimerization of these terminal alkynes to 2,4-disubstituted but-1-en-3-ynes (head-to-tail dimers). This implies that the known dimerization of 1-alkynes in the presence of [(η5-C5Me4R1)2Ti(η2-Me3SiC⋮CSiMe3)] (R1 = H, Me) performed in diffuse daylight is initiated by the

  许多取代的二茂钛-炔基-烯基配合物，[（η 5 -C 5我4 - [R 1）2的Ti（η 1 -C⋮CR 2）（η 1 - （Ë）-CH CHR 2）]（R 1 = H，Me中的pH值，的Bz; R 2 = CME 3，森达3，二茂铁基;甲型复合物），由相应的双（三甲硅基）乙炔络合物反应得到[（η 5 -C 5我4 - [R 1）2的Ti（η 2 -Me3 SiC⋮CSiMe 3）]与1炔烃R 2 C⋮CH在黑暗中于60°C混合。复合物经受在暴露的碳基配体的偶联于阳光，得到二茂钛配合物的1,4-二取代丁-1-烯-3-炔，[（η 5 -C 5我4 - [R 1）2的Ti（3， 4-η-R 2 ç⋮CCH CHR 2）]（乙型配合物）。与A型配合物在黑暗中不会与过量的叔丁基乙炔和（三甲基甲硅烷基）乙炔进一步反应的相反，B型复合物诱导这些末端炔烃快速二聚为2，4-二取代的but-1-en-3-y