(η⁵-C₅Me₄SiMe₃)₂TiCH₃ | 944272-12-2

• 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: (η⁵-C₅Me₄SiMe₃)₂TiCH₃
• 英文别名: methylbis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(III)；carbanide;titanium(3+);trimethyl-(2,3,4,5-tetramethylcyclopenta-1,3-dien-1-yl)silane
• CAS: 944272-12-2
• 化学式: C₂₅H₄₅Si₂Ti
• 分子量: 449.683
• InChiKey: FVLQXWRVXXPWIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.82
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (η⁵-C₅Me₄SiMe₃)₂TiCH₃ 以 甲苯 为溶剂， 以85%的产率得到(η(5):η(1)-C5Me4SiMe2CH2)(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti
  参考文献：
  名称：

  Effect of the Trimethylsilyl Substituent on the Reactivity of Permethyltitanocene

  摘要：

  The presence of a trimethylsilyl substituent in place of one of the methyl groups of each of the cyclopentadienyl ligands of decamethyltitanocene enhances the thermal stability of the resulting complex, [Ti-II{eta(5)-C5Me4(SiMe3)}(2)] (1), and controls the products formed in thermolysis of its methyl derivatives. Titanocene 1 was found to be stable in toluene solution up to 90 degrees C, while under vacuum at 140 degrees C it liberated hydrogen to give the asymmetrical doubly tucked-in titanocene [Ti-II{eta(3):eta(4)-C5Me2(SiMe3)(CH2)(2)}{eta(5)-C5Me4(SiMe3)}] (3). The mono- and dimethyl derivatives of 1, the complexes [(TiMe)-Me-III{eta(5)-C5Me4(SiMe3)}(2)] (5) and [(TiMe2)-Me-IV{eta(5)-C5Me4(SiMe3)}(2)] (6), undergo thermolysis at lower temperature than do the corresponding permethyltitanocene derivatives and eliminate hydrogen from their trimethylsilyl group. Thus, the known [Ti-III{eta(5):eta(1)-C5Me4(SiMe2CH2)}{eta(5)-C5Me4(SiMe3)}] (4) was obtained from 5, and compound 6 afforded [Ti-II{eta(6):eta(1)-C5Me3(CH2)(SiMe2CH2)}{eta(5)-C5Me4(SiMe3)}] (7) at only 90 degrees C, both with liberation of methane. Crystal structures of 3, 5, and 7 were determined. DFT calculations for titanocene 1 revealed that the metal-cyclopentadienyl bonding is accomplished via a three-center-four-electron orbital interaction. An auxiliary long-range Si-C bond interaction with the Ti center was also established, providing a reason for the enhanced thermal stability of 1. The molecular orbitals participating in the exo methylene-titanium bonds for 3 and 7 are also three-centered and are compatible with the assignment of their activated ligands to eta(3):eta(4)-allyldiene and eta(6)-fulvene structures, respectively. Qualitatively, the much higher thermal stability of 3 and 7 compared to that of 1 is due to the exploitation of four d orbitals in the bonding molecular orbitals for 3 and 7 versus only two d orbitals for 1.

  DOI：

  10.1021/om070159l
• 作为产物：
  描述：

  (η5-C5Me4SiMe3)2TiCl 、 甲基锂 以 甲苯 、 正戊烷 为溶剂， 反应 12.0h， 以72%的产率得到(η⁵-C₅Me₄SiMe₃)₂TiCH₃
  参考文献：
  名称：

  使用质子耦合电子转移氢解钛-氮键合成氨

  摘要：

  描述了 (η(5)-C5Me4SiMe3)2Ti(Cl)NH2 中钛-酰胺键的催化氢解以产生游离氨。氢化铑 (η(5)-C5Me5)(py-Ph)RhH（py-Ph = 2-苯基吡啶）作为催化剂，通过氢原子转移促进 NH 键的形成。还测定了二茂钛和二茂锆配合物的氨配体的 NH 键解离自由能，并揭示了对金属特性和氧化态的明显依赖性。在所有情况下，配位 NH3 的 NH BDFE 比游离气相分子中的值降低了 >40 kcal/mol。

  DOI：

  10.1021/jacs.5b01047