CpCr[DppNC(Me)CHC(Me)NTol] | 1262528-60-8

• 英文名称: CpCr[DppNC(Me)CHC(Me)NTol]
• 英文别名: [(cyclopentadienyl)Cr(II)(2,6-(Me2CH)2C6H3NC(Me)CH(Me)NC6H4Me)]；[CpCr(DppNC(Me)CHC(Me)NC6H4Me)]
• CAS: 1262528-60-8
• 化学式: C₂₉H₃₆CrN₂
• 分子量: 464.614
• InChiKey: XPKTYPVFDDDURJ-VUDHPSJJSA-N

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：

  CpCr[DppNC(Me)CHC(Me)NTol] 、 碘 以 乙醚 为溶剂， 以40%的产率得到[(cyclopentadienyl)Cr(III)I(2,6-(Me2CH)2C6H3NC(Me)CH(Me)NC6H4Me)]
  参考文献：
  名称：

  Electronic Effects in the Oxidative Addition of Iodomethane with Mixed-Aryl β-Diketiminate Chromium Complexes

  摘要：

  The Cr-II complexes CpCr[DppNC(Me)CHC(Me)NC6H4Y] (1; Dpp = 2,6-(Me2CH)(2)C6H3) were used to prepare the corresponding Cr-III iodo (2) and methyl (3) mixed-aryl beta-diketiminate compounds with Y = OMe (a), CH3 (b), H (c), CF3 (d). Oxidation of the Cr-II precursors with iodine gave CpCr[DppNC(Me)CHC(Me)NC6H4Y](I) (2a-d). The Cr-III methyl compounds 3a-d were prepared by reaction of the Cr-II complexes with iodomethane followed by MeMgI. The Cr-III chloride complexes 4a-d were synthesized by salt metathesis of isolated CpCrCl2(THF) with the appropriate deprotonated mixed-aryl beta-diketiminate. The structures of the paramagnetic complexes 1b,c, 2a,b, 3a-d, and 4a-d were determined by single-crystal X-ray diffraction. The rate constants for the single-electron oxidative addition of iodomethane with 1a-d were determined by monitoring the reaction by UV-vis spectroscopy. The rate constants correlated well with the electronic parameters of the Y substituents (rho = -0.36). The rate constants for 1a-d were an order of magnitude greater than those previously obtained for the same reaction with CpCr[(DppNCMe)(2)CH] and related ortho-disubstituted symmetric beta-diketiminate complexes.

  DOI：

  10.1021/om100961f
• 作为产物：
  描述：

  sodium cyclopentadienide 、 chromium dichloride 、 2-(2,6-diisopropylphenyl)amino-4-(4-methylphenyl)imino-2-pentene 在 C₄H₉Li 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以81%的产率得到CpCr[DppNC(Me)CHC(Me)NTol]
  参考文献：
  名称：

  Electronic Effects in the Oxidative Addition of Iodomethane with Mixed-Aryl β-Diketiminate Chromium Complexes

  摘要：

  The Cr-II complexes CpCr[DppNC(Me)CHC(Me)NC6H4Y] (1; Dpp = 2,6-(Me2CH)(2)C6H3) were used to prepare the corresponding Cr-III iodo (2) and methyl (3) mixed-aryl beta-diketiminate compounds with Y = OMe (a), CH3 (b), H (c), CF3 (d). Oxidation of the Cr-II precursors with iodine gave CpCr[DppNC(Me)CHC(Me)NC6H4Y](I) (2a-d). The Cr-III methyl compounds 3a-d were prepared by reaction of the Cr-II complexes with iodomethane followed by MeMgI. The Cr-III chloride complexes 4a-d were synthesized by salt metathesis of isolated CpCrCl2(THF) with the appropriate deprotonated mixed-aryl beta-diketiminate. The structures of the paramagnetic complexes 1b,c, 2a,b, 3a-d, and 4a-d were determined by single-crystal X-ray diffraction. The rate constants for the single-electron oxidative addition of iodomethane with 1a-d were determined by monitoring the reaction by UV-vis spectroscopy. The rate constants correlated well with the electronic parameters of the Y substituents (rho = -0.36). The rate constants for 1a-d were an order of magnitude greater than those previously obtained for the same reaction with CpCr[(DppNCMe)(2)CH] and related ortho-disubstituted symmetric beta-diketiminate complexes.

  DOI：

  10.1021/om100961f
• 作为试剂：
  描述：

  溴代环己烷 、 四苯基二膦 在 锰 、 CpCr[DppNC(Me)CHC(Me)NTol] 、 lead(II) bromide 作用下， 以 四氢呋喃 为溶剂， 反应 28.0h， 以70%的产率得到二苯基环己基膦
  参考文献：
  名称：

  Controlling Secondary Alkyl Radicals: Ligand Effects in Chromium-Catalyzed C–P Bond Formation

  摘要：

  Chromium cyclopentadienyl beta-diketiminate catalysts have been used to form Ph2PCy from Ph2PY (Y = Cl, PPh2, H) and CyX (X = Br, Cl) substrates. Manganese powder activated by PbX2 or Me3SiCl was used as the stoichiometric reductant. The Cr(III) cyclohexyl intermediate has been synthesized and structurally characterized. The observed variations in catalytic activity have been correlated with the previously observed reactivity differences imparted by modifying the N-aryl substituents on the beta-diketiminate ancillary ligand.

  DOI：

  10.1021/om300846u