| 118418-59-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• CAS: 118418-59-0
• 化学式: 4Al*6CH₃*2C₆H₁₂NO₃
• 分子量: 490.467
• InChiKey: KCZSOWZKJRJNTQ-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  [Fe(η(6)-1,3,5-trimethylbenzene)2](PF6)2 、 以 1,2-二氯乙烷 为溶剂， 以39%的产率得到((C6H3Me3)(C6H3Me4)Fe)PF6
  参考文献：
  名称：

  烷基铝试剂与有机过渡金属芳烃配合物的相互作用：将烷基化物，卤代烷基化物和二氯甲基净添加到[（arene）2Fe] 2+阳离子中

  摘要：

  AlEt3 reacts with the hexafluorophosphate salts of Ar2Fe2+ cations (Ar = arene = benzene (1a), p-xylene (1b), mesitylene (1c), pentamethylbenzene (1d), hexamethylbenzene (1e)) in dichloromethane or 1,2-dichloroethane to afford ChArFe+ (Ch = cyclohexadienyl) cations. The major products, the hexafluorophosphate salts of 2a-e, result from net Et- addition to a single arene ring. The corresponding reactions with AlMe3 in CH2X2 (X = Cl, Br) are more complex and afford characterizable products for 1c,e only. The unexpected major products of these reactions are the hexafluorophosphate salts of the [(6-CH2X-Ch)ArFe]+ monocations 3c,e (X = Cl) and 4c,e (X = Br), derived from net addition of CH2X, rather than the expected methide addition products, 5a-e. 1c reacts with [N(CH2CH2O)3Al2Me3]2 (6), a compound that contains an octahedral aluminum methyl moiety, in dichloromethane to produce yet another ChArFe+ species, (eta(5)-exo-6-(dichloromethyl)-1,3,5-trimethylcyclohexadienyl)(eta(6)-mesitylene)iron(II) hexafluorophosphonate (7c[PF6]), which is the result of net addition of CHCl2-. The methide addition monocationic product 5c[PF6] can be prepared in low yield from AlMe3 or 6 and 1c if benzene and 1,2-dichloroethane, respectively, are utilized as solvent. The relevance of these reactions is discussed in the general context of transition-metal activation of Ar molecules. In addition to spectroscopic characterization, several compounds were characterized by X-ray crystallography. Full crystallographic details of the CH2Cl-Ch and CHCl2-Ch cations 3c and 7c, respectively, are presented and discussed in the context of related ChFe compounds: 3c[PF6], orthorhombic, Pcab, with a = 15.2496 (9) angstrom, b = 15.5537 (10) angstrom, c = 17.5146 (16) angstrom, Z = 8, R = 0.059, R(w) = 0.058 for 2506 independent, observed (I > 2.5-sigma(I)), and absorption-corrected reflections; 7c[PF6].(CH3)2CO, monoclinic, P2(1)/c, with a = 18.762 (3) angstrom, b = 8.758 (2) angstrom, c = 17.104 (3) angstrom, beta = 113.40 (2)-degrees, Z = 4, R = 0.049, R(w) = 0.055 for 2051 independent, observed (I > 2.5-sigma(I)), and absorption-corrected reflections.

  DOI：

  10.1021/om00037a057
• 作为产物：
  描述：

  trimethylaluminum 、 三乙醇胺 以 苯 为溶剂， 生成
  参考文献：
  名称：

  烷基铝试剂与有机过渡金属芳烃配合物的相互作用：将烷基化物，卤代烷基化物和二氯甲基净添加到[（arene）2Fe] 2+阳离子中

  摘要：

  AlEt3 reacts with the hexafluorophosphate salts of Ar2Fe2+ cations (Ar = arene = benzene (1a), p-xylene (1b), mesitylene (1c), pentamethylbenzene (1d), hexamethylbenzene (1e)) in dichloromethane or 1,2-dichloroethane to afford ChArFe+ (Ch = cyclohexadienyl) cations. The major products, the hexafluorophosphate salts of 2a-e, result from net Et- addition to a single arene ring. The corresponding reactions with AlMe3 in CH2X2 (X = Cl, Br) are more complex and afford characterizable products for 1c,e only. The unexpected major products of these reactions are the hexafluorophosphate salts of the [(6-CH2X-Ch)ArFe]+ monocations 3c,e (X = Cl) and 4c,e (X = Br), derived from net addition of CH2X, rather than the expected methide addition products, 5a-e. 1c reacts with [N(CH2CH2O)3Al2Me3]2 (6), a compound that contains an octahedral aluminum methyl moiety, in dichloromethane to produce yet another ChArFe+ species, (eta(5)-exo-6-(dichloromethyl)-1,3,5-trimethylcyclohexadienyl)(eta(6)-mesitylene)iron(II) hexafluorophosphonate (7c[PF6]), which is the result of net addition of CHCl2-. The methide addition monocationic product 5c[PF6] can be prepared in low yield from AlMe3 or 6 and 1c if benzene and 1,2-dichloroethane, respectively, are utilized as solvent. The relevance of these reactions is discussed in the general context of transition-metal activation of Ar molecules. In addition to spectroscopic characterization, several compounds were characterized by X-ray crystallography. Full crystallographic details of the CH2Cl-Ch and CHCl2-Ch cations 3c and 7c, respectively, are presented and discussed in the context of related ChFe compounds: 3c[PF6], orthorhombic, Pcab, with a = 15.2496 (9) angstrom, b = 15.5537 (10) angstrom, c = 17.5146 (16) angstrom, Z = 8, R = 0.059, R(w) = 0.058 for 2506 independent, observed (I > 2.5-sigma(I)), and absorption-corrected reflections; 7c[PF6].(CH3)2CO, monoclinic, P2(1)/c, with a = 18.762 (3) angstrom, b = 8.758 (2) angstrom, c = 17.104 (3) angstrom, beta = 113.40 (2)-degrees, Z = 4, R = 0.049, R(w) = 0.055 for 2051 independent, observed (I > 2.5-sigma(I)), and absorption-corrected reflections.

  DOI：

  10.1021/om00037a057