Ti(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)2 | 475975-29-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Ti(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)2
• CAS: 475975-29-2
• 化学式: C₉₂H₁₁₆O₈Si₂Ti
• 分子量: 1453.98
• InChiKey: UTRATWDGJKHQQZ-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  23.42
• 重原子数：
  103.0
• 可旋转键数：
  0.0
• 环数：
  20.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  73.84
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为产物：
  描述：

  [(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)Ti(OC(p-MeC6H4)2C(p-MeC6H4)2O)] 以 氘代甲苯 为溶剂， 生成 、 Ti(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)2
  参考文献：
  名称：

  Mechanistic Insight into Fragmentation Reactions of Titanapinacolate Complexes

  摘要：

  Reactions between terminal alkynes or aromatic ketones and titanapinacolate complexes (DMSC)Ti(OCAr(2)CAr(2)O) (2, Ar = Ph, and 3, At = p-MeC(6)H(4); DMSC = 1,2-alternate dimethylsilyl-bridged p-tertbutylcalix[4]arene dianion) occur via rupture of the C-C bond of the titanacycle. Thus, reactions of 2 and 3 with terminal alkynes produce 2-oxatitanacyclopent-4-ene or 2-oxatitanacycloheptadiene complexes along with free Ar(2)CO. These compounds have been characterized spectroscopically and by X-ray crystallography. Because metallapinacolate intermediates have been implicated in important C-C bond-forming reactions, such as pinacol coupling and McMurry chemistry, the mechanism of the fragmentation reactions was studied. Analysis of the kinetics of the reaction of (DMSC)Ti{OC(p-MeC(6)H(4))(2)C(p-MeC(6)H(4))(2)O} (3) with Bu(t)C=CH revealed that the fragmentation reactions proceed via a preequilibrium mechanism, involving reversible dissociation of titanapinacolate complexes into (DMSC)Ti(eta(2)-OCAr(2)) species with release of a ketone molecule, followed by rate-limiting reaction of (DMSC)Ti(eta(2)-OCAr(2)) species with an alkyne or ketone molecule.

  DOI：

  10.1021/ja0271577