(1,2,3-Me3allyl)MgBr | 109929-24-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: (1,2,3-Me3allyl)MgBr
• CAS: 109929-24-0
• 化学式: C₆H₁₁BrMg
• 分子量: 187.362
• InChiKey: QJHLTOJFNOFZFJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.78
• 重原子数：
  8.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  CpHfCl3*2THF 、 (1,2,3-Me3allyl)MgBr 以 乙醚 为溶剂， 以54%的产率得到(cyclopentadienyl)Hf(1,2,3-Me₃allyl)(1,2-Me₂butadiene)
  参考文献：
  名称：

  Cyclopentadienyl(allyl)(butadiene)hafnium compounds. Synthesis, crystal structure, and dynamics of cyclopentadienyl(1,2,3-trimethylallyl)(1,2-dimethylbutadiene)hafnium and cyclopentadienyl(1,1,2-trimethylallyl)(2,3-dimethylbutadiene)hafnium

  摘要：

  The reaction of CpHfCl3.2THF with 2 equiv of (1,2,3-Me3allyl)MgBr or (1,1,2-Me3allyl)MgBr yields Cp(1,2,3-Me3allyl)(1,2-Me2butadiene)Hf (3) or Cp(1,1,2-Me3allyl)(2,3-Me2butadiene)Hf (4). X-ray crystallography of 3 shows that both the allyl and butadiene ligands assume a prone orientation with respect to Cp. For 3: cell constants a = 15.109 (5), b = 7.150 (2), c = 15.587 (6) angstrom, beta = 115.41 (1)degrees; space group P2(1)/c; R = 0.0305, R(w) = 0.0347. Variable-temperature H-1 NMR studies indicate that compound 3 is static on the NMR time scale whereas 4 exists in two isomeric forms and undergoes three separate dynamic processes involving eta-3-eta-1 isomerization at the unsubstituted and substituted ends of the allyl ligand [DELTA-G double-ended-dagger = 39.4 +/- 1.0 kJ/mol and 73.4 +/- 1.0 kJ/mol, respectively] and butadiene flip [DELTA-G double-ended-dagger (avg) = 49.8 +/- 1.0 kJ/mol].

  DOI：

  10.1021/om00050a033

文献信息

• Larson, Erlund J.; Van Dort, Paul C.; Dailey, James S., Organometallics, 1987, vol. 6, # 10, p. 2141 - 2146
  作者：Larson, Erlund J.、Van Dort, Paul C.、Dailey, James S.、Lakanen, John R.、Pederson, Lori M.、Silver, Michael E.、Huffman, John C.、Russo, Steven O.

  DOI：——

  日期：——
• Hafnium halide compounds of methyl substituted allyl ligands. Synthesis, crystal structure and dynamics of (η5-C5Me5)(η3-1,2,3-Me3allyl)HfBr2 and (η5-C5Me5)(η3-1,1,2-Me3allyl)HfBr2
  作者：Bryan E. Hauger、Peter J. Vance、Thomas J. Prins、Michael E. Wemple、David A. Kort、Michael E. Silver、John C. Huffman

  DOI：10.1016/s0020-1693(00)82981-3

  日期：1991.9

  The reaction of Cp*HfCl3 with (1,2,3-Me3allyl)MgBr or (1,1,2-Me3allyl)MgBr and excess MgBr2 yields Cp*(1,2,3-Me3allyl)HfBr2 and Cp*(1,1,2-Me3allyl)HfBr2. X-ray crystallography of these compounds shows a bent-metallocene-type geometry, with steric congestion in the asymmetrically methylated compound causing the greatest distortion yet observed of an eta-3-allyl ligand towards an eta-1-binding mode for an early-transition metal complex. For Cp*(1,2,3-Me3allyl)HfBr2: cell constants a = 14.581(7), b = 14.725(8), c = 8.291(3) angstrom; space group Pcmn; R = 0.0425, R(w) = 0.0397. For Cp*(1,1,2-Me3allyl)HfBr2: cell constants a = 9.158(2), b = 13.141(4), c = 14.575(3) angstrom, beta = 101.06(2)-degrees; space group P2(1)/n; R = 0.0383, R(w) = 0.0401. A variable temperature H-1 NMR study indicates that the allyl ligand in (1,1,2-Me3allyl)HfBr2 undergoes eta-3-eta-1 isomerization (DELTA-G double-ended dagger(-53-degrees-C) = 40.9 +/- 1 kJ/mol).
• Larson, Erlund J.; Van Dort, Paul C.; Lakanen, John R., Organometallics, 1988, vol. 7, # 5, p. 1183 - 1187
  作者：Larson, Erlund J.、Van Dort, Paul C.、Lakanen, John R.、O'Neill, Daniel W.、Pederson, Lori M.、McCandless, Jill J.、Silver, Michael E.、Russo, Steven O.、Huffman, John C.

  DOI：——

  日期：——