[(η5-cyclopentadienyl)2Zr(η2-CH2NMePh)][MeB(C6F5)3] | 403503-05-9

• 英文名称: [(η5-cyclopentadienyl)2Zr(η2-CH2NMePh)][MeB(C6F5)3]
• CAS: 403503-05-9
• 化学式: C₁₈H₂₀NZr*C₁₉H₃BF₁₅
• 分子量: 868.607
• InChiKey: YMQRRAFYDMHOLB-UHFFFAOYSA-N

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：

  四氢呋喃 、 [(η5-cyclopentadienyl)2Zr(η2-CH2NMePh)][MeB(C6F5)3] 以 四氢呋喃 、 氘代苯 为溶剂， 生成 [(cyclopentadienyl)2Zr(η2-CH2NMe(C6H5))(THF)][MeB(C6F5)3]
  参考文献：
  名称：

  Synthesis, Characterization, Interionic Structure, and Self-Aggregation Tendency of Zirconaaziridinium Salts Bearing Long Alkyl Chains

  摘要：

  Zirconaaziridinium inner sphere ion pairs (ISIPs) bearing alkyl chains of different lengths, [Cp2Zr(eta(2)-(CH2NRR2)-R-1)(+)center dot center dot center dot X-] (R-1 = Me, R-2 = C2H5, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NC2; R-1 = me, R-2 = C16H33, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NC16; R-1 = R-2 = C18H37, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NC18; R-1 = Me, R-2 = Ph, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NPh; R-1 = R-2 = C18H37, X- = B(C6F5)(4)(-), (ZrBT)-B-NC18; R-1 = Me, R-2 = Ph, X- = B(C6F5)(4)(-), (ZrBT)-B-NPh), have been synthesized by the reaction of [Cp2ZrMe+center dot center dot center dot MeB(C6F5)(3)(-)] or [CP2ZrMe+center dot center dot center dot B(C6F5)(4)(-)] with the suitable tertiary amine followed by selective C-H activation of one Me group of the coordinated amine and methane elimination. Subsequent reaction of ISIPs with THF afforded the corresponding outer-sphere ion pairs (OSIPs) ([(ZrTHF)-T-NC2][BN], [(ZrTHF)-T-NC16][BN], [(ZrTHF)-T-NC18][BN], [(ZrTHF)-T-NPh][BN], [(ZrTHF)-T-NC18][BT], [(ZrTHF)-T-NPh][BT]) in which the anion has been displaced into the second coordination sphere. The interionic structure in solution (i.e., the relative cation-anion position) and the self-aggregation level of both ISIPs and OSIPs have been investigated by means of H-1 NOESY, F-19, H-1 HOESY, and diffusion PGSE NMR methods, in low polar solvents. It is found that, independent of the nature or length of the alkyl chains, the anion prefers to pair with the cation from the side of the nitrogen atom and THF in ISIPs and OSIPs, respectively. Self-aggregation of ion pairs into higher aggregates is also weakly influenced by the nature of the alkyl chains, but it is strictly connected with the nature of the counterion: ISIPs and OSIPs bearing B(C6F5)(4)(-) showed an increased tendency to form higher aggregates with respect to those containing MeB(C6F5)(3)(-). The level of the self-aggregation in benzene-d(6) and cyclohexane-d(12) has been quantified by fitting the hydrodynamic volumes obtained from NMR diffusion experiments with several models of indefinite self-association. The IK model, in which the equilibrium constants slightly increase on increasing the aggregation step, best describes the experimental trends in all cases. The standard Gibbs free energy of self-association at 297 K (Delta G(0)) for (ZrBN)-B-NC18 is -6.7 +/- 0.2 kJ mol(-1) and -12.6 +/- 0.7 kJ mol(-1) in benzene-d(6) and cyclohexane-d(12), respectively. In the same solvents, the values of Delta G(0) are -17.9 +/- 0.5 kJ mol(-1) and -25.0 +/- 0.3 kJ mol(-1) for [(ZrTHF)-T-NC18][BT].At room temperature, 80% and 4% of [(ZrTHF)-T-NC18][BT]are present in the form of ion pairs in cyclohexane-d(12) at analytical concentrations of 10(-5) and 10(-3) M, respectively. The self-aggregation of [(ZrTHF)-T-NC18][BN] in cyclohexane-d(12) is strongly depressed by increasing the temperature.

  DOI：

  10.1021/om100827z
• 作为产物：
  描述：

  N,N-二甲基苯胺 、 [(C5H5)2Zr(CH3)(μ-H3C)B(C6F5)3] 以 氘代苯 为溶剂， 生成 [(η5-cyclopentadienyl)2Zr(η2-CH2NMePh)][MeB(C6F5)3]
  参考文献：
  名称：

  Synthesis, Characterization, Interionic Structure, and Self-Aggregation Tendency of Zirconaaziridinium Salts Bearing Long Alkyl Chains

  摘要：

  Zirconaaziridinium inner sphere ion pairs (ISIPs) bearing alkyl chains of different lengths, [Cp2Zr(eta(2)-(CH2NRR2)-R-1)(+)center dot center dot center dot X-] (R-1 = Me, R-2 = C2H5, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NC2; R-1 = me, R-2 = C16H33, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NC16; R-1 = R-2 = C18H37, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NC18; R-1 = Me, R-2 = Ph, X- = MeB(C6F5)(3)(-), (ZrBN)-B-NPh; R-1 = R-2 = C18H37, X- = B(C6F5)(4)(-), (ZrBT)-B-NC18; R-1 = Me, R-2 = Ph, X- = B(C6F5)(4)(-), (ZrBT)-B-NPh), have been synthesized by the reaction of [Cp2ZrMe+center dot center dot center dot MeB(C6F5)(3)(-)] or [CP2ZrMe+center dot center dot center dot B(C6F5)(4)(-)] with the suitable tertiary amine followed by selective C-H activation of one Me group of the coordinated amine and methane elimination. Subsequent reaction of ISIPs with THF afforded the corresponding outer-sphere ion pairs (OSIPs) ([(ZrTHF)-T-NC2][BN], [(ZrTHF)-T-NC16][BN], [(ZrTHF)-T-NC18][BN], [(ZrTHF)-T-NPh][BN], [(ZrTHF)-T-NC18][BT], [(ZrTHF)-T-NPh][BT]) in which the anion has been displaced into the second coordination sphere. The interionic structure in solution (i.e., the relative cation-anion position) and the self-aggregation level of both ISIPs and OSIPs have been investigated by means of H-1 NOESY, F-19, H-1 HOESY, and diffusion PGSE NMR methods, in low polar solvents. It is found that, independent of the nature or length of the alkyl chains, the anion prefers to pair with the cation from the side of the nitrogen atom and THF in ISIPs and OSIPs, respectively. Self-aggregation of ion pairs into higher aggregates is also weakly influenced by the nature of the alkyl chains, but it is strictly connected with the nature of the counterion: ISIPs and OSIPs bearing B(C6F5)(4)(-) showed an increased tendency to form higher aggregates with respect to those containing MeB(C6F5)(3)(-). The level of the self-aggregation in benzene-d(6) and cyclohexane-d(12) has been quantified by fitting the hydrodynamic volumes obtained from NMR diffusion experiments with several models of indefinite self-association. The IK model, in which the equilibrium constants slightly increase on increasing the aggregation step, best describes the experimental trends in all cases. The standard Gibbs free energy of self-association at 297 K (Delta G(0)) for (ZrBN)-B-NC18 is -6.7 +/- 0.2 kJ mol(-1) and -12.6 +/- 0.7 kJ mol(-1) in benzene-d(6) and cyclohexane-d(12), respectively. In the same solvents, the values of Delta G(0) are -17.9 +/- 0.5 kJ mol(-1) and -25.0 +/- 0.3 kJ mol(-1) for [(ZrTHF)-T-NC18][BT].At room temperature, 80% and 4% of [(ZrTHF)-T-NC18][BT]are present in the form of ion pairs in cyclohexane-d(12) at analytical concentrations of 10(-5) and 10(-3) M, respectively. The self-aggregation of [(ZrTHF)-T-NC18][BN] in cyclohexane-d(12) is strongly depressed by increasing the temperature.

  DOI：

  10.1021/om100827z

文献信息

• Low-Temperature Kinetic NMR Studies on the Insertion of a Single Olefin Molecule into a ZrC Bond: Assessing the Counterion-Solvent Interplay
  作者：Luca Rocchigiani、Gianluca Ciancaleoni、Cristiano Zuccaccia、Alceo Macchioni

  DOI：10.1002/anie.201105122

  日期：2011.12.2

  Sticky counterions: Low‐temperature kinetic NMR studies were performed to determine ΔH≠ and ΔS≠ values for the insertion of a single 2‐methyl‐1‐heptene molecule into a ZrC bond of [Cp2Zr(η2‐CH2NMePh)][X] (1a: X−=MeB(C6F5)3−, 1b: B(C6F5)4−) in [D8]toluene and a 1:1 mixture of [D8]toluene and [D5]chlorobenzene. Both activation parameters critically depend on the interplay of the counterion and the solvent

  粘抗衡离子：低温动力学NMR进行研究以确定Δ ħ ≠和Δ小号≠值插入单2-甲基-1-庚烯分子的成锆 [Cp的C键2的Zr（η 2 - CH 2 NMePh）] [X]（1A：X - = MEB（C 6 ˚F 5）3 - ，1B：B（C 6 ˚F 5）4 - ）在[d 8 ]甲苯和1：1的混合物[ D 8 ]甲苯和[D 5]氯苯。两种活化参数都主要取决于抗衡离子和溶剂的相互作用。