[Ti(C5Me5)((t-Bu)3PN)(Br)][B(C6F5)4] | 700846-84-0

• 英文名称: [Ti(C5Me5)((t-Bu)3PN)(Br)][B(C6F5)4]
• 英文别名: [Cp(*)((t)Bu3P=N)TiBr][B(C6F5)4]
• CAS: 700846-84-0
• 化学式: C₂₂H₄₂BrNPTi*C₂₄BF₂₀
• 分子量: 1158.38
• InChiKey: ZWEMPAGSXBLDAS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  四氢呋喃 、 [Ti(C5Me5)((t-Bu)3PN)(Br)][B(C6F5)4] 以 四氢呋喃 为溶剂， 生成 [Ti(C5Me5)((t-Bu)3PN)(Br)(THF)][B(C6F5)4]
  参考文献：
  名称：

  Competitive ArC−H and ArC−X (X = Cl, Br) Activation in Halobenzenes at Cationic Titanium Centers

  摘要：

  The titanium methyl cation [Cp*((Bu3P)-Bu-t=N)TiCH3](+)[B(C6F5)(4)](-) reacts rapidly with H-2 to give the analogous cationic hydride [Cp*((Bu3P)-Bu-t=N)TiH(THF)(n)](+)[B(C6F5)(4)](-) (n = 0, 1), which can be trapped and isolated as its THF adduct 1 (.) THF (n = 1). When generated in the presence of chloro or bromobenzene, 1 undergoes C-X activation or ortho-C-H activation, depending on the amount of dihydrogen present in the reaction medium. At similar to 4 atm of H-2, C-X activation is preferred, giving the halocations [Cp*((Bu3P)-Bu-t=N)TiX](+)[B(C6F5)(4)](-) (2X) and C6H6/biphenyl mixtures. At lower pressures of H-2 (> 1 atm), the beta-halophenyl cations [Cp*((Bu3P)-Bu-t=N)Ti(2-X-C6H4)](+)[B(C6F5)(4)](-) (3X) are the products isolated. In the absence of H-2, these compounds are quite thermally stable, but undergo beta-halogen elimination upon moderate heating, to give 2X (similar to 20%) and compounds U which are the result of reaction between 2X and benzyne via addition of the benzyne C-C triple bond across the Ti-N bond of the phosphinimide ligand. Thus, three separate bond activation processes are operative in this system: direct C-X activation, ortho-C-H activation, and indirect C-X activation via beta-halogen elimination. Mechanistic studies on all three processes have been done and support a radical pathway for direct C-X cleavage, sigma-bond metathesis of the ortho-C-H bond Of eta(1)-coordinated C6H5X, and beta-halogen elimination from base-free compound 3X.

  DOI：

  10.1021/ja0583618
• 作为产物：
  描述：

  [Cp(*)((t)Bu3P=N)Ti(2-Br-C6H4)][B(C6F5)4] 以 not given 为溶剂， 以55%的产率得到
  参考文献：
  名称：

  Competitive ArC−H and ArC−X (X = Cl, Br) Activation in Halobenzenes at Cationic Titanium Centers

  摘要：

  The titanium methyl cation [Cp*((Bu3P)-Bu-t=N)TiCH3](+)[B(C6F5)(4)](-) reacts rapidly with H-2 to give the analogous cationic hydride [Cp*((Bu3P)-Bu-t=N)TiH(THF)(n)](+)[B(C6F5)(4)](-) (n = 0, 1), which can be trapped and isolated as its THF adduct 1 (.) THF (n = 1). When generated in the presence of chloro or bromobenzene, 1 undergoes C-X activation or ortho-C-H activation, depending on the amount of dihydrogen present in the reaction medium. At similar to 4 atm of H-2, C-X activation is preferred, giving the halocations [Cp*((Bu3P)-Bu-t=N)TiX](+)[B(C6F5)(4)](-) (2X) and C6H6/biphenyl mixtures. At lower pressures of H-2 (> 1 atm), the beta-halophenyl cations [Cp*((Bu3P)-Bu-t=N)Ti(2-X-C6H4)](+)[B(C6F5)(4)](-) (3X) are the products isolated. In the absence of H-2, these compounds are quite thermally stable, but undergo beta-halogen elimination upon moderate heating, to give 2X (similar to 20%) and compounds U which are the result of reaction between 2X and benzyne via addition of the benzyne C-C triple bond across the Ti-N bond of the phosphinimide ligand. Thus, three separate bond activation processes are operative in this system: direct C-X activation, ortho-C-H activation, and indirect C-X activation via beta-halogen elimination. Mechanistic studies on all three processes have been done and support a radical pathway for direct C-X cleavage, sigma-bond metathesis of the ortho-C-H bond Of eta(1)-coordinated C6H5X, and beta-halogen elimination from base-free compound 3X.

  DOI：

  10.1021/ja0583618

文献信息

• Isolation and Characterization of a Monomeric Cationic Titanium Hydride
  作者：Kuangbiao Ma、Warren E. Piers、Yuan Gao、Masood Parvez

  DOI：10.1021/ja048952i

  日期：2004.5.1

  with H2 to form a cationic Ti(IV) hydride species, 4, which was resistant to reduction. While only moderately stable in solution under H2, a stable, isolable THF adduct preciptitated upon addition of THF, giving 4.THF, which was fully characterized, including via X-ray crystallography. Naked hydride 4 was very reactive toward haloarene solvents such as bromobenzene, giving the cationic bromide [Cp*

  由三叔丁基膦亚胺配体和 C5H5 或 C5Me5 稳定的甲基阳离子 1-Cp 和 1-Cp* 由中性二甲基前体和 [Ph3C]+[B(C6F5)4]-生成。这些化合物与H 2 的反应导致相反的反应。对于 1-Cp，Ti-CH3 基团的氢解导致快速还原为 Ti(III) 并产生阳离子 Ti(III) 二聚体 2，可能是在瞬时生成的 Ti(IV) 氢化物失去 H2 时形成的。化合物 2 的晶体学特征是通过其与供体溶剂如 THF 裂解形成单体 [Cp(L)Ti(THF)2]+[B( )4]-, 3。相反，1-Cp* 反应与 H2 迅速形成阳离子 Ti(IV) 氢化物物质 4，它具有抗还原性。虽然在 H2 溶液中仅适度稳定，但加入 THF 后会沉淀出稳定、可分离的 THF 加合物，给出 4.THF，它被充分表征，包括通过 X 射线晶体学。裸氢化物 4 对卤代芳烃溶剂（如溴苯）的反应性很强，得到阳离子溴化物