Cp(*)((t)Bu3P=N)Ti(CH3)Cl | 882534-82-9

• 英文名称: Cp(*)((t)Bu3P=N)Ti(CH3)Cl
• CAS: 882534-82-9
• 化学式: C₂₃H₄₅ClNPTi
• 分子量: 449.924
• InChiKey: HPWBVVDJYNGZHS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Cp(*)((t)Bu3P=N)Ti(CH3)Cl 、 三苯碳四(五氟苯基)硼酸盐 以 further solvent(s) 为溶剂， 生成 [Cp(*)((t)Bu3P=N)TiCl][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：

  [(η5-C5Me5)TiMe2(NP(C(CH3)3)3)] 、 [(η5-C5Me5)TiCl2(NP((CH3)3C)3)] 在 B(C₆F₅)3 作用下， 以 甲苯 为溶剂， 以76%的产率得到Cp(*)((t)Bu3P=N)Ti(CH3)Cl
  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