[(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)Ti(OC(p-MeC6H4)2C(p-MeC6H4)2O)] | 305819-51-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)Ti(OC(p-MeC6H4)2C(p-MeC6H4)2O)]
• 英文别名: Ti(OC(p-MeC6H4)2C(p-MeC6H4)2O)(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)
• CAS: 305819-51-6
• 化学式: C₇₆H₈₆O₆SiTi
• 分子量: 1171.48
• InChiKey: GOLAWMQKAGJUQR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  18.78
• 重原子数：
  84.0
• 可旋转键数：
  4.0
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  4,4'-二甲基二苯甲酮 、 (C6H2(C(CH3)3)CH2O)4Ti(Si(CH3)2)(η6-1,2,4-C6H3(Si(CH3)3)3) 以 正庚烷 为溶剂， 以92%的产率得到[(1,2-alternate dimethylsilyl-bridged p-tert-butylcalix[4]arene dianion)Ti(OC(p-MeC6H4)2C(p-MeC6H4)2O)]
  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

文献信息

• Synthesis and Reactivity of [(DMSC)Ti(η²-OCAr₂)L₂] Complexes (DMSC = Dimethylsilyl-Bridged <i>p-tert-</i>Butylcalix[4]arene Dianion, Ar = Aryl Group, and L₂ = Delocalized Diimine)
  作者：Jesudoss V. Kingston、Vallipuram Sarveswaran、Sean Parkin、Folami T. Ladipo

  DOI：10.1021/om020487f

  日期：2003.1.1

  dmbpy, or phen). The ketone is weakly bound in 3−6, and it is readily dissociated. The compounds dissolve in aromatic hydrocarbon solvents to give intense green solutions and undergo a photochemically assisted transformation into 1-aza-5-oxa-titanacyclopentene derivatives 8−11, in which C−H activation of the heterocyclic diimine ligand and hydride migration to a Ti-bound ketone to form an alkoxide group

  钛萘那考酯配合物[（DMSC）Ti（OCAr 2 CAr 2 O）]（1，Ar = Ph; 2，Ar = p -MeC 6 H 4的反应; DMSC = 1,2-Alternate dimethylsilylbridged- p- tert - butylcalix [4]芳烃二价阴离子）与1个当量离域二亚胺布置钛η的2 -酮配合物[（DMSC）的Ti（η 2 -OCAr 2）L- 2）] 3 - 6（L 2 =联吡啶，dmbpy，或phen）的。酮在3 − 6中弱结合，并且很容易解离。化合物溶解在芳族烃溶剂，得到深绿色溶液，并进行光化学辅助转化成1-氮杂-5-氧杂titanacyclopentene衍生物8 - 11，杂环二亚胺的配体，其中C-H活化和氢化物迁移到钛发生键合的酮形成醇盐基团。的反应3 - 6与适当的酮的一个或多个当量，得到8 - 11以高收率。将化合物用NMR（1 H和13为[（DMSC）的Ti