Dimethyl-prop-2-enyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane | 359442-51-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Dimethyl-prop-2-enyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane
• CAS: 359442-51-6
• 化学式: C₁₄H₂₄Si
• 分子量: 220.43
• InChiKey: OTSIZBNOJLGLTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.94
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Dimethyl-prop-2-enyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane 、 bis(tetrahydrofuran)tris(trimethylsilylmethyl)yttrium(III) 以 氘代苯 为溶剂， 以90%的产率得到dimethyl-prop-2-enyl-(2,3,4,5-tetramethylcyclopenta-1,3-dien-1-yl)silane;methanidyl(trimethyl)silane;oxolane;yttrium(3+)
  参考文献：
  名称：

  环戊二烯基烯烃的双去质子化反应，形成多齿三阴离子环戊二烯基烯丙基配体体系。

  摘要：

  DOI：

  10.1021/ja004320u
• 作为产物：
  描述：

  氯丙烯镁 、 二甲基氯(2,3,4,5-四甲基-2,4-环戊二烯-1-基)硅烷 以 乙醚 为溶剂， 反应 6.0h， 以82%的产率得到Dimethyl-prop-2-enyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane
  参考文献：
  名称：

  环戊二烯基烯烃的双去质子化反应，形成多齿三阴离子环戊二烯基烯丙基配体体系。

  摘要：

  DOI：

  10.1021/ja004320u

文献信息

• Reduction-Induced Cyclization and Redox Reactions of Fully Methylated Titanocene Dichlorides Bearing Pendant Alkenyldimethylsilyl Groups, [TiCl₂{η⁵-C₅Me₄(SiMe₂R)}₂] (R = Vinyl and Allyl)
  作者：Lenka Lukešová、Petr Štěpnička、Karla Fejfarová、Róbert Gyepes、Ivana Císařová、Michal Horáček、Jiří Kubišta、Karel Mach

  DOI：10.1021/om020150d

  日期：2002.6.1

  Reduction of titanocene dichlorides bearing (omega-alkenyl)dimethylsilyl substituents [TiCl2eta(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 [Tieta(2):eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (7) and the product of a hydrogen loss, the doubly tethered; paramagnetic eta(3)-allyl Ti(III) complex [Tieta(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 [TiXeta:(5)eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (X = Cl, 12; OMe, 13). Oxidation of 8 with PbCl2 yields eta(1)-alkenyl complex [TiCleta(1):eta(5):eta5-C5Me4SiMe2CH(Ti)CH=CHCH2SiMe2C5Me4}] (11). A similar oxidation of 12 to ansa-titanocene dichloride [TiCl2eta:(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.
• Double Deprotonation of a Cyclopentadienyl Alkene to Form a Polydentate Trianionic Cyclopentadienyl Allyl Ligand System
  作者：William J. Evans、Jason C. Brady、Joseph W. Ziller

  DOI：10.1021/ja004320u

  日期：2001.8.1