CpFe(C5H4COCH2CH(Ph)O)TiClCp2 | 171818-35-2

• 英文名称: CpFe(C5H4COCH2CH(Ph)O)TiClCp2
• CAS: 171818-35-2
• 化学式: C₂₉H₂₇ClFeO₂Ti
• 分子量: 546.712
• InChiKey: YDHYFBODFKYFIB-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：

  CpFe(C5H4COCH2CH(Ph)O)TiClCp2 、 四苯硼钠 以 二氯甲烷 为溶剂， 以83%的产率得到[CpFe(C5H4COCH2CH(Ph)O)TiCp2][BPh4]
  参考文献：
  名称：

  钛和锆二茂铁取代的烯酸酯及其与苯甲醛和苯乙酮的反应产物：醛醇缩合途径的结构和动力学研究

  摘要：

  The reaction of acetyl- and propionylferrocene, [(RCOcp)(cp)Fe] (R = Me (1), Et (2)), with KH led to the isolation of the corresponding ion-pair enolates 3 and a in the solid state. When the deprotonation of 1 is carried out in the presence of 18-crown-6, the naked enolate 5, [(CH(2)COcp)(cp)Fe]K--(18-crown-6)(+)], was isolated. The potassium enolate 3 has been converted into the corresponding titanium and zirconium enolates via the reaction with (cp)(2)MCl(2) (M = Ti, Zr), while only 4 was converted into the analogous zirconium enolate. The following metal enolates have been isolated in good yield and as crystalline solids: [(cp)-Fe(cpC(CH2)O)M(cp)(2)(Cl)] (M = Ti (6), Zr (7)) and [(cp)Fe(cpC(CHMe)O)Zr(cp)(2)(Cl)] (8). Compounds 6 and 7 have been characterized by H-1 and C-13 NMR, and an X-ray crystal structure of 7 was obtained; compound 8 was characterized by H-1 NMR. The aldol reaction of 6 and 7 with benzaldehyde led to the corresponding metal aldol derivatives [(cp)Fe(cpC-(O)CH2C(H)(Ph)O)M(cp)(2)(Cl)] (M = Ti (9), Zr(10)). For compound 9 the solid-state structure and solution data are reported. Complex 9 undergoes a facile Ti-Cl ionization, leading to the cationic complex [(cp)Fe(cpC(O)CH2C(H)(Ph)O)Ti(cp)(2)](+)BPh(4)(-) (11). In complex 11, the aldol fragment forms a metallacycle where both oxygens are bonded to titanium. This structure mimics the bond connectivity of the generally proposed ''transition state'' of aldol reactions. The isolation of structurally well-defined titanium and zirconium enolates allowed us to carry out a kinetic investigation into the reaction of 7 with acetophenone. The reaction was carried out in C6D6 at temperatures from 283 to 340 K. The reaction is second order (first order in each reactant), and the following activation parameters have been obtained: Delta H-double dagger = 44.4 +/- 1.7 kJ mol(-1), Delta S-double dagger greater than or equal to -150 +/- 6 J mol(-1) K-1, and Delta G(298)(double dagger) = 89.0 +/- 2.4 kJ mol(-1). A similar study with 4-fluoroacetophenone gave Delta H-double dagger = 33.0 +/- 4.6 kJ mol(-1), Delta S-double dagger greater than or equal to -189 +/- 15 J mol(-1) K-1, and Delta G(298)(double dagger) = 89.2 +/- 6.4 kJ mol(-1). The reaction rate at 320 K determined with 4-chloro-, 4-methyl-, and 4-nitroacetophenone allowed the determination of a Hammett plot with rho = 0.42 +/- 0.9. This value is implicit for a carbon-carbon bond-forming, rate-limiting step. Complexes 7 and 9 have been characterized by X-ray analysis.

  DOI：

  10.1021/om00009a013
• 作为产物：
  描述：

  CpFe(C5H4C(=CH2)O)TiClCp2 、 苯甲醛 以 甲苯 为溶剂， 以73%的产率得到CpFe(C5H4COCH2CH(Ph)O)TiClCp2
  参考文献：
  名称：

  钛和锆二茂铁取代的烯酸酯及其与苯甲醛和苯乙酮的反应产物：醛醇缩合途径的结构和动力学研究

  摘要：

  The reaction of acetyl- and propionylferrocene, [(RCOcp)(cp)Fe] (R = Me (1), Et (2)), with KH led to the isolation of the corresponding ion-pair enolates 3 and a in the solid state. When the deprotonation of 1 is carried out in the presence of 18-crown-6, the naked enolate 5, [(CH(2)COcp)(cp)Fe]K--(18-crown-6)(+)], was isolated. The potassium enolate 3 has been converted into the corresponding titanium and zirconium enolates via the reaction with (cp)(2)MCl(2) (M = Ti, Zr), while only 4 was converted into the analogous zirconium enolate. The following metal enolates have been isolated in good yield and as crystalline solids: [(cp)-Fe(cpC(CH2)O)M(cp)(2)(Cl)] (M = Ti (6), Zr (7)) and [(cp)Fe(cpC(CHMe)O)Zr(cp)(2)(Cl)] (8). Compounds 6 and 7 have been characterized by H-1 and C-13 NMR, and an X-ray crystal structure of 7 was obtained; compound 8 was characterized by H-1 NMR. The aldol reaction of 6 and 7 with benzaldehyde led to the corresponding metal aldol derivatives [(cp)Fe(cpC-(O)CH2C(H)(Ph)O)M(cp)(2)(Cl)] (M = Ti (9), Zr(10)). For compound 9 the solid-state structure and solution data are reported. Complex 9 undergoes a facile Ti-Cl ionization, leading to the cationic complex [(cp)Fe(cpC(O)CH2C(H)(Ph)O)Ti(cp)(2)](+)BPh(4)(-) (11). In complex 11, the aldol fragment forms a metallacycle where both oxygens are bonded to titanium. This structure mimics the bond connectivity of the generally proposed ''transition state'' of aldol reactions. The isolation of structurally well-defined titanium and zirconium enolates allowed us to carry out a kinetic investigation into the reaction of 7 with acetophenone. The reaction was carried out in C6D6 at temperatures from 283 to 340 K. The reaction is second order (first order in each reactant), and the following activation parameters have been obtained: Delta H-double dagger = 44.4 +/- 1.7 kJ mol(-1), Delta S-double dagger greater than or equal to -150 +/- 6 J mol(-1) K-1, and Delta G(298)(double dagger) = 89.0 +/- 2.4 kJ mol(-1). A similar study with 4-fluoroacetophenone gave Delta H-double dagger = 33.0 +/- 4.6 kJ mol(-1), Delta S-double dagger greater than or equal to -189 +/- 15 J mol(-1) K-1, and Delta G(298)(double dagger) = 89.2 +/- 6.4 kJ mol(-1). The reaction rate at 320 K determined with 4-chloro-, 4-methyl-, and 4-nitroacetophenone allowed the determination of a Hammett plot with rho = 0.42 +/- 0.9. This value is implicit for a carbon-carbon bond-forming, rate-limiting step. Complexes 7 and 9 have been characterized by X-ray analysis.

  DOI：

  10.1021/om00009a013