Zr(acetylene) | 156734-25-7

• 英文名称: Zr(acetylene)
• 英文别名: Zr-η2-(C2H2)
• CAS: 156734-25-7
• 化学式: C₂H₂Zr
• 分子量: 117.262
• InChiKey: FWWOHXZKBBVQOO-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：

  Zr(acetylene) 、 乙烯 以 gaseous matrix 为溶剂， 生成 Zr(acetylene)2 、 氢气
  参考文献：
  名称：

  H₂ Elimination Products from Neutral Zr + Alkene Reactions in the Gas Phase

  摘要：

  Identification of the metal-containing products of reactions of the neutral transition metal atom Zr(4d(2)5s(2), F-3) with ethylene and propylene is accomplished using one-photon ionization at 157 nm and time-of-flight mass spectrometry, The reactions proceed in a fast flow reactor at 298 K with He/N-2 buffer gas at 0.6 Torr. Mass spectra of the products of both Zr + C2H4 and Zr + C3H6 indicate that H-2 elimination occurs as the primary reaction step. The efficiency of the Zr + C2H4 reaction shows that there is no barrier larger than about 2 kcal/mol above reactants along the entire reaction path. This corroborates an earlier theoretical prediction by Blomberg and Siegbahn of facile H-2 elimination by ground-state Zr. For the secondary reactions ZrC2H2 + C2H4 and ZrC3H4 + C3H6 and for the reactions ZrO + C2H4 and ZrO + C3H6, mass spectra again indicate that H-2 elimination occurs. Rate constant measurements using photoionization detection show that the presence of the C2H2 and C3H4 ligands enhances the reaction efficiency over that of thr bare Zr atom, while ZrO reacts at essentially the same rate as Zr.

  DOI：

  10.1021/jp9825617
• 作为产物：
  描述：

  锆 在 C₂H₄ 作用下， 以 neat (no solvent) 为溶剂， 生成 Zr(acetylene)
  参考文献：
  名称：

  氘同位素对基态 Zr 与乙烯和丙烯反应速率的影响

  摘要：

  Zr (4d 2 5s 2 , 3 F) 与 C2H4 和 C2D4 以及与 C3H6 和 C3D6 的反应的动力学同位素效应是在 300 K 的快流反应器中测量的，其中 He/N2 缓冲气体为 0.8 Torr。使用 157 nm 的单光子电离和飞行时间质谱法检测 H2 和 D2 消除产物。我们发现与乙烯或丙烯的反应没有显着的同位素效应。这些结果显然有利于间接机制涉及将金属原子添加到 CC 双键和随后的 CH 插入，并排除了最近提出的涉及在低碰撞能量下直接插入 CH 键的机制。B3LYP/LANL2DZ 形式的密度泛函理论没有发现将基态 Zr 添加到乙烯双键上的障碍，并证实了从金属环丙烷配合物到 H2 产物的低能路径的存在。Theory 还提供了一组现实的几何形状和振动频率，用于热金属环丙烷复合物衰变的统计速率模型。然而，RRKM 计算表明，Zr 和乙烯接近的小障碍（0.5-2 kcal/mol）对于解释我们的动力学数据和

  DOI：

  10.1021/jp993082q

文献信息

• Reaction Dynamics of Zr and Nb with Ethylene
  作者：Peter A. Willis、Hans U. Stauffer、Ryan Z. Hinrichs、H. Floyd Davis

  DOI：10.1021/jp9846633

  日期：1999.5.1

  The reactions of transition metal (M) atoms Zr and Nb with ethylene (C2H4) were studied using the technique of crossed molecular beams. Angular and velocity distributions of MC2H2 products following H-2 elimination were measured at collision energies between 5 and 23 kcal/mol using electron impact and 157 nm photoionization mass spectrometry. Photodepletion studies identify that the atomic reactants are predominantly in their ground electronic states and that the observed MC2H2 products result primarily from reactions of these ground-state atoms. Center-of-mass product angular distributions derived from the data indicate that reactions involve the formation of intermediate complexes having lifetimes longer than their rotational periods. Product translational energy distributions demonstrate that a large fraction of excess available energy is channeled into product internal excitation. Wide-angle nonreactive scattering of metal atom reactants following decay of long-lived MC2H4 association complexes was also observed for both transition metal reactants at collision energies greater than or equal to 9 kcal/mol, with approximately 36% of the initial translational energy converted into C2H4 internal excitation. At collision energies of less than or equal to 6 kcal/mol, nonreactive scattering of Zr from ZrC2H4 decay was found to be negligible, whereas this channel was clearly observed for Nb. RRKM modeling of the competition between decay of MC2H4 complexes back to M + C2H4 and C-H insertion forming HMC2H3 indicates that there exists an adiabatic potential energy barrier for M + C2H4 association in the case of Zr and that the transition state for this process is tighter than for the analogous process in Nb + C2H4. The barrier for Zr + C2H4 association is attributed to the repulsive s(2) ground state configuration of Zr, whereas for Nh the s(1) ground state configuration results in no barrier for association. The absence of decay of ZrC2H4 back to Zr + C2H4 at low collision energies indicates that the barrier for C-H insertion forming HZrC2H3 lies below the barrier for Zr + C2H4 association. This opens up the possibility that direct C-H insertion without initial ZrC2H4 formation may play an important role.