bis(η5-1,2-dimethylcyclopentadienyl)dichlorotitanium | 73364-21-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: bis(η5-1,2-dimethylcyclopentadienyl)dichlorotitanium
• 英文别名: [(η5-C5H3-1,2-Me2)2TiCl2]；bis(dimethylcyclopentadienyl)dichlorotitan；1,5-Dimethylcyclopenta-1,3-diene;titanium(4+);dichloride；1,5-dimethylcyclopenta-1,3-diene;titanium(4+);dichloride
• CAS: 73364-21-3
• 化学式: C₁₄H₁₈Cl₂Ti
• 分子量: 305.083
• InChiKey: KUYFPDRAFIXWSZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.95
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(η5-1,2-dimethylcyclopentadienyl)dichlorotitanium 、 甲基锂 以 乙醚 为溶剂， 以77%的产率得到[(η5-C5H3-1,2-Me2)2TiMe2]
  参考文献：
  名称：

  钛茂与双取代的环戊二烯基配体的侧对二氮配合物：合成，结构和光谱表征。

  摘要：

  所述1,3-二取代二茂钛络合物的还原，（η 5 -C 5 H ^ 3 -1,3-我镨2）2 TII或外消旋，内消旋- （η 5 -C 5 H ^ 3 -1-我PR-3 -Me）2 TII，具有N下过量0.5％钠汞齐2气氛提供的相应的二茂钛化合物二氮，[（η 5 -C 5 H ^ 3 -1,3-我镨2）2的Ti] 2（μ 2， η2，η 2 -N 2）和[（η 5 -C 5 H ^ 3 -1-我PR-3-Me）中的Ti] 2（μ 2，η 2，η 2 -N 2）。对这两种分子的晶体学研究表明，[N 2 ] 2-配体侧向结合，其N–N距离分别为1.226（5）和1.216（5）Å。可变温度磁化率研究确定了环境温度下三重态基态的种群，其能量略高于单重态。减少1,3-环戊二烯基的取代基的大小，以甲基，[（η 5 -C 5ħ 3 -1,3-ME 2）2的Ti]，导致结晶的三金属钛二氮复合物与活化μ 3，η

  DOI：

  10.1021/om300156z
• 作为产物：
  描述：

  1,2-二甲基-1,3-环戊二烯 、 三氯化钛 在 n-butyllithium 作用下， 以 四氢呋喃 、 正己烷 、 甲醚 为溶剂， 以46%的产率得到bis(η5-1,2-dimethylcyclopentadienyl)dichlorotitanium
  参考文献：
  名称：

  Importance of steric requirements relative to electronic contributions in bicycloalkyl-substituted titanocene dichlorides

  摘要：

  A group of bicycloalkyl-substituted titanocene dichlorides was examined by X-ray photoelectron spectroscopy in order to gauge if the rather large steric requirements of these ligands exert greater or lesser impact on the binding energy of the titanium center relative to the electronic effect of alkyl substitution. Simpler model systems were likewise evaluated. X-ray crystallographic data were available for many of the norbornyl-, bornyl-, and pinanyl-fused titanocenes. The solid-state structure of 3 has been established by X-ray crystallographic analysis: space group C2/c, a = 12.456(5), b = 6.695(3), c = 16.591(8) angstrom; beta = 98.37(3)-degrees; Z = 4. The structure refined to R and R(w) values of 0.067 and 0.079, respectively, with use of 1357 reflections. This information and associated Fenske-Hall calculations revealed that, although heightened levels of ring slippage were in effect, the inductive contributions of substituents directly bonded to the Cp rings dominate over the steric contributions of the space-demanding ligands in controlling the electronic changes at the core titanium atom.

  DOI：

  10.1021/om00013a022

文献信息

• Importance of steric requirements relative to electronic contributions in bicycloalkyl-substituted titanocene dichlorides
  作者：Bruce E. Bursten、Matthew R. Callstrom、Cynthia A. Jolly、Leo A. Paquette、Mark R. Sivik、Roy S. Tucker、Charles A. Wartchow

  DOI：10.1021/om00013a022

  日期：1994.1

  A group of bicycloalkyl-substituted titanocene dichlorides was examined by X-ray photoelectron spectroscopy in order to gauge if the rather large steric requirements of these ligands exert greater or lesser impact on the binding energy of the titanium center relative to the electronic effect of alkyl substitution. Simpler model systems were likewise evaluated. X-ray crystallographic data were available for many of the norbornyl-, bornyl-, and pinanyl-fused titanocenes. The solid-state structure of 3 has been established by X-ray crystallographic analysis: space group C2/c, a = 12.456(5), b = 6.695(3), c = 16.591(8) angstrom; beta = 98.37(3)-degrees; Z = 4. The structure refined to R and R(w) values of 0.067 and 0.079, respectively, with use of 1357 reflections. This information and associated Fenske-Hall calculations revealed that, although heightened levels of ring slippage were in effect, the inductive contributions of substituents directly bonded to the Cp rings dominate over the steric contributions of the space-demanding ligands in controlling the electronic changes at the core titanium atom.
• Side-on Dinitrogen Complexes of Titanocenes with Disubstituted Cyclopentadienyl Ligands: Synthesis, Structure, and Spectroscopic Characterization
  作者：Scott P. Semproni、Carsten Milsmann、Paul J. Chirik

  DOI：10.1021/om300156z

  日期：2012.5.14

  activated μ3,η2,η1,η1-N2 ligand with an N–N distance of 1.320(3) Å. Hydrogenation of the isomeric titanocene dimethyl complex, (η5-C5H3-1,2-Me2)2TiMe2, in the presence of dinitrogen did not result in N2 coordination but rather furnished the bimetallic titanium compound, (η5-C5H3-1,2-Me2)2Ti(μ2-H)Ti(η5-C5H3-1,2-Me2)(η5,η1-C5H2-1,2-Me2), resulting from C–H activation of a cyclopentadienyl ring position. Addition

  所述1,3-二取代二茂钛络合物的还原，（η 5 -C 5 H ^ 3 -1,3-我镨2）2 TII或外消旋，内消旋- （η 5 -C 5 H ^ 3 -1-我PR-3 -Me）2 TII，具有N下过量0.5％钠汞齐2气氛提供的相应的二茂钛化合物二氮，[（η 5 -C 5 H ^ 3 -1,3-我镨2）2的Ti] 2（μ 2， η2，η 2 -N 2）和[（η 5 -C 5 H ^ 3 -1-我PR-3-Me）中的Ti] 2（μ 2，η 2，η 2 -N 2）。对这两种分子的晶体学研究表明，[N 2 ] 2-配体侧向结合，其N–N距离分别为1.226（5）和1.216（5）Å。可变温度磁化率研究确定了环境温度下三重态基态的种群，其能量略高于单重态。减少1,3-环戊二烯基的取代基的大小，以甲基，[（η 5 -C 5ħ 3 -1,3-ME 2）2的Ti]，导致结晶的三金属钛二氮复合物与活化μ 3，η