(E)-BrMgCH=CHMe

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (E)-BrMgCH=CHMe
• 英文别名: magnesium;prop-1-ene;bromide
• 化学式: Br*C₃H₅Mg
• 分子量: 145.282
• InChiKey: WQMNNHNWITXOAH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -2.38
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (η5-pentamethylcyclopentadienyl)(η6-tetramethylfulvene) titanium chloride 、 (E)-BrMgCH=CHMe 以 四氢呋喃 为溶剂， 以34%的产率得到(E)-η(5)-C5Me5 tetramethyl fulvene Ti 1-propenyl methyl
  参考文献：
  名称：

  Isomerization of an η³-Allyl to an (E)-1-Propenyl in (C₅Me₅)(C₅Me₄CH₂)TiC₃H₅:  Mechanism, Kinetics, and Thermodynamics

  摘要：

  The isomerization of Cp*FvTi(eta(3)-C3H5) (1) to Cp*FvTi((E)-CH=CHMe) (5) proceeds through four intermediates, Cp*Ti-2(eta 2-allene) (2), two geometrical isomers of Cp*FvTiCMe=CH2 (3a,b), and Cp*Ti-2(eta(2)-propyne) (4) (Cp*, C5Me5; Fv, C5Me4CH2). The process was monitored at four temperatures between 10 and 40 degrees C starting from 1 or the mixture 3a,b. The time-dependent concentration profiles of all compounds were simulated with a mathematical model of 10 rate constants. The model is based on the assumption that the isomerization proceeds through reversible first-order reaction steps in the sequence 1 reversible arrow 2 reversible arrow 3a reversible arrow 3b reversible arrow 4 reversible arrow 5. Equilibrium constants yield Gibbs free energy differences between the complexes ranging from 0 to -8 kJ/mol. The activation enthalpies for the forward reactions lie between 75 and 102 kJ/mol and between 74 and 111 kJ/mol for the reverse reactions. The entropy of activation is negative for the forward and reverse reactions between 1 and 2 and between 4 and 5 and positive for transitions involving the sterically congested isomers 3a,b, except for the rotation of the isopropenyl group in 3a.

  DOI：

  10.1021/ja972867b