[Ti(η1:η1:η5:η5-C5(CH3)4(Si(CH3)2CH(Ti)CH2CH2CH(Ti)Si(CH3)2C5(CH3)4)] | 443889-11-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [Ti(η1:η1:η5:η5-C5(CH3)4(Si(CH3)2CH(Ti)CH2CH2CH(Ti)Si(CH3)2C5(CH3)4)]
• 英文别名: 4-[dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl]butyl-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane;titanium(4+)
• CAS: 443889-11-0
• 化学式: C₂₆H₄₂Si₂Ti
• 分子量: 458.67
• InChiKey: ILGBQHZIEJTCNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.39
• 重原子数：
  29
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [Ti(η1:η1:η5:η5-C5(CH3)4(Si(CH3)2CH(Ti)CH2CH2CH(Ti)Si(CH3)2C5(CH3)4)] 以 氘代苯 为溶剂， 生成 [Ti(η5-C5(CH3)4(Si(CH3)2CHCH2))(η2:η5-C5(CH3)4(Si(CH3)2CHCH2))]
  参考文献：
  名称：

  Reduction-Induced Cyclization and Redox Reactions of Fully Methylated Titanocene Dichlorides Bearing Pendant Alkenyldimethylsilyl Groups, [TiCl₂{η⁵-C₅Me₄(SiMe₂R)}₂] (R = Vinyl and Allyl)

  摘要：

  Reduction of titanocene dichlorides bearing (omega-alkenyl)dimethylsilyl substituents [TiCl2{eta(5)-C5Me5(SiMe2R)}(2)], where R = CH=CH2 (3) and CH2CH=CH2 (4), affords highly reactive Ti(II) intermediates, which immediately undergo intramolecular reactions with the pendant double bonds in a way dependent on the length of the alkenyl chain. The reduction of 4 with magnesium at 60 degreesC affords cleanly the cyclopentadienyl-ring-tethered titanacyclopentane, [Ti(eta(1):eta(1):eta(5):eta(5)-C5Me4SiMe2CH(Ti)CH(Me)CH(Me)CH(Ti)SiMe2C5Me4](5), which can be opened by HCl to an ansa-titanocene dichloride with a six-membered saturated bridging chain, [TiCl2-{eta:(5)eta(5)-C5Me4SiMe2CH2CH(Me)CH(Me)CH2SiMe2C5Me4)(2)}] (6). An analogous reaction of 3 can be accomplished at low temperatures and only to some extent, providing a mixture of titanacyclopentane complex [Ti(eta(1):eta(1):eta(5):eta(5)-C5Me4SiMe2CH(Ti)CH2CH2CH(Ti)SiMe2C5Me4] (10) and the fluxional eta(2)-alkene complex [Ti(eta(5)-C5Me4SiMe2CH=CH2)(eta(2):eta(5)-C5Me4SiMe2CH=CH2)1 (9). At 60 degreesC, the reduction of 3 yields a mixture of ansa-eta(2)-alkene complex [Ti{eta(2):eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (7) and the product of a hydrogen loss, the doubly tethered; paramagnetic eta(3)-allyl Ti(III) complex [Ti{eta(3):eta(5):eta(5)-C5Me4SiMe2CHCH=CHCH2SiMe2C5Me4}] (8). When the reduction of 3 with magnesium is carried out in the presence of bis(trimethylsilyl)ethyne as the proton acceptor, 8 is obtained as the sole isolated product. Complex 8 reacts with protic reagents such as HCl and methanol under protonation/decomplexation of the allyl system to give the d(1) paramagnetic complexes [TiX{eta:(5)eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (X = Cl, 12; OMe, 13). Oxidation of 8 with PbCl2 yields eta(1)-alkenyl complex [TiCl{eta(1):eta(5):eta5-C5Me4SiMe2CH(Ti)CH=CHCH2SiMe2C5Me4}] (11). A similar oxidation of 12 to ansa-titanocene dichloride [TiCl2{eta:(5)eta-C5Me4SiMe2CHCH=CHCH2SiMe2C5Me4}] (14) containing a symmetrical unsaturated bridging chain requires a stronger oxidizing agent, AgCl. Compounds 5, 7, 8, and 10-14 have been characterized by X-ray crystallography.

  DOI：

  10.1021/om020150d
• 作为产物：
  描述：

  [TiCl2(η5-C5(CH3)4(Si(CH3)2CHCH2))2] 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 以30%的产率得到[Ti(η5-C5(CH3)4(Si(CH3)2CHCH2))(η2:η5-C5(CH3)4(Si(CH3)2CHCH2))]
  参考文献：
  名称：

  Reduction-Induced Cyclization and Redox Reactions of Fully Methylated Titanocene Dichlorides Bearing Pendant Alkenyldimethylsilyl Groups, [TiCl₂{η⁵-C₅Me₄(SiMe₂R)}₂] (R = Vinyl and Allyl)

  摘要：

  Reduction of titanocene dichlorides bearing (omega-alkenyl)dimethylsilyl substituents [TiCl2{eta(5)-C5Me5(SiMe2R)}(2)], where R = CH=CH2 (3) and CH2CH=CH2 (4), affords highly reactive Ti(II) intermediates, which immediately undergo intramolecular reactions with the pendant double bonds in a way dependent on the length of the alkenyl chain. The reduction of 4 with magnesium at 60 degreesC affords cleanly the cyclopentadienyl-ring-tethered titanacyclopentane, [Ti(eta(1):eta(1):eta(5):eta(5)-C5Me4SiMe2CH(Ti)CH(Me)CH(Me)CH(Ti)SiMe2C5Me4](5), which can be opened by HCl to an ansa-titanocene dichloride with a six-membered saturated bridging chain, [TiCl2-{eta:(5)eta(5)-C5Me4SiMe2CH2CH(Me)CH(Me)CH2SiMe2C5Me4)(2)}] (6). An analogous reaction of 3 can be accomplished at low temperatures and only to some extent, providing a mixture of titanacyclopentane complex [Ti(eta(1):eta(1):eta(5):eta(5)-C5Me4SiMe2CH(Ti)CH2CH2CH(Ti)SiMe2C5Me4] (10) and the fluxional eta(2)-alkene complex [Ti(eta(5)-C5Me4SiMe2CH=CH2)(eta(2):eta(5)-C5Me4SiMe2CH=CH2)1 (9). At 60 degreesC, the reduction of 3 yields a mixture of ansa-eta(2)-alkene complex [Ti{eta(2):eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (7) and the product of a hydrogen loss, the doubly tethered; paramagnetic eta(3)-allyl Ti(III) complex [Ti{eta(3):eta(5):eta(5)-C5Me4SiMe2CHCH=CHCH2SiMe2C5Me4}] (8). When the reduction of 3 with magnesium is carried out in the presence of bis(trimethylsilyl)ethyne as the proton acceptor, 8 is obtained as the sole isolated product. Complex 8 reacts with protic reagents such as HCl and methanol under protonation/decomplexation of the allyl system to give the d(1) paramagnetic complexes [TiX{eta:(5)eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (X = Cl, 12; OMe, 13). Oxidation of 8 with PbCl2 yields eta(1)-alkenyl complex [TiCl{eta(1):eta(5):eta5-C5Me4SiMe2CH(Ti)CH=CHCH2SiMe2C5Me4}] (11). A similar oxidation of 12 to ansa-titanocene dichloride [TiCl2{eta:(5)eta-C5Me4SiMe2CHCH=CHCH2SiMe2C5Me4}] (14) containing a symmetrical unsaturated bridging chain requires a stronger oxidizing agent, AgCl. Compounds 5, 7, 8, and 10-14 have been characterized by X-ray crystallography.

  DOI：

  10.1021/om020150d