(η6-C6H6)Cr(CO)2(H2) | 127446-51-9

• 英文名称: (η6-C6H6)Cr(CO)2(H2)
• 英文别名: (C6H6)Cr(CO)2(η2-H2)；(η6-benzene)Cr(CO)2(hydrogen)
• CAS: 127446-51-9
• 化学式: C₈H₈CrO₂
• 分子量: 188.146
• InChiKey: NQYUXHXBTXBMSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 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

• 作为产物：
  描述：

  苯三羰基铬 在 hydrogen 作用下， 以 further solvent(s) 为溶剂， 生成 (η6-C6H6)Cr(CO)2(H2)
  参考文献：
  名称：

  Organometallic chemistry in supercritical fluids. The generation and detection of dinitrogen and nonclassical dihydrogen complexes of Group 6, 7, and 8 transition metals at room temperature

  摘要：

  DOI：

  10.1021/ja00168a027

文献信息

• Coordination of molecular nitrogen and hydrogen to (.eta.6-C6H6)Cr(CO)x and (.eta.5-C5H5)Mn(CO)x (x = 2 and 1) in the gas phase
  作者：Youfeng Zheng、Wenhua Wang、Jingu Lin、Yongbo She、Kejian Fu

  DOI：10.1021/j100203a045

  日期：1992.11

  Time-resolved infrared absorption spectroscopy is used to study the coordination reactions of N2 and H-2 with photolytically generated coordinatively unsaturated species (eta6-C6H6)Cr(CO)x and (eta5-C5H5)Mn(CO)x (x = 2 and 1) in the gas phase. Additions of N2 and H-2 to (eta6-C6H6)Cr(CO)2 and (eta5-C5H5)Mn(CO)2 form corresponding molecular nitrogen and hydrogen complexes. Additions of N2 and H-2 to (eta6-C6H6)Cr(CO) are confirmed although no product absorption is observed. By comparison, reactions of N2 and H-2 with (eta5-C5H5)Mn(CO) are not observed, presumably due to spectral overlap. The rate constants for reactions of N2 and H-2 With (eta6-C6H6)Cr(CO)2 and (eta5-C5H5)Mn(CO)2 as well as with (eta6-C6H6)Cr(CO) are measured, and an upper limit for the rate constants for reactions of N2 and H-2 with (eta5-C5H5)Mn(CO) is estimated. Significant differences are observed for the rate constants for reactions of different species and discussed with respect to spin-allowed versus disallowed processes.
• Energetics of the Reactions of <b>(</b>η⁶-C₆H₆)Cr(CO)₃ with <i>n</i>-Heptane, N₂, and H₂ Studied by High-Pressure Photoacoustic Calorimetry
  作者：Eoin F. Walsh、Michael W. George、Simon Goff、Sergei M. Nikiforov、Vladimir K. Popov、Xue-Zhong Sun、Martyn Poliakoff

  DOI：10.1021/jp9621686

  日期：1996.1.1

  The enthalpy changes associated with the photosubstitution of (eta(6)-C6H6)Cr(CO)(3) by n-heptane, H-2, and N-2 have been measured by high-pressure photoacoustic calorimetry (PAC). The kinetics of the reaction of (eta(6)-C6H6)Cr(CO)(3) to form (eta(6)-C6H6)Cr(CO)(2)L (L = H-2 and N-2) under high pressures of H-2 and N-2 have been monitored by time-resolved infrared spectroscopy (TRIR), showing that the increased concentration of ligand at high pressure greatly accelerates the reaction, making it possible to use the PAC technique to study these reactions. PAC experiments in n-heptane show the enthalpy change for the reaction of (eta(6)-C6H6)Cr(CO)(3) + H-2 --> (eta(6)-C6H6)Cr(CO)(2)(eta(2)-H-2) + CO to be +91 +/- 4 kJ mol(-1). The PAC data indicate that the strength of the Cr-L bond in (eta(6)-C6H6)Cr(CO)(2)L (L = H-2 and N-2) is similar to that in the corresponding Cr(CO)(5)L complexes. We estimate the Cr-H-2 bond dissociation enthalpy (BDE) in (eta(6)-C6H6)Cr(CO)(2)(eta(2)-H-2) to be 60 +/- 4 kJ mol(-1) and the Cr-N-2 BDE to be 6 kJ mol(-1) stronger (66 +/- 4 kJ mol(-1)). The thermal equilibrium between (eta(6)-C6H6)Cr(CO)(2)(eta(2)-H-2) and (eta(6)-C6H6)Cr(CO)(2)(N-2) was studied by FTIR in a polyethylene matrix pressurized with a mixture of H-2 and N-2 (130 bar). Conversion of (eta 6-C6H6)Cr(Co)(2)(N-2) to (eta(6)-C6H6)Cr(CO)(2)(eta(2)-H-2) was achieved by using a high pressure of H-2 at 22 degrees C.