cobalt-rhodium heptacarbonyl

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: cobalt-rhodium heptacarbonyl
• 化学式: 7CO*Co*Rh
• 分子量: 357.971
• InChiKey: WHDQEMVDSRGNIT-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：

  cobalt-rhodium heptacarbonyl 在 一氧化碳 、 氢气 作用下， 以 正己烷 为溶剂， 生成 dodecacarbonyltetrarhodium(0) 、 cobalt tetracarbonyl hydride
  参考文献：
  名称：

  CoRh（CO）7存在下Co / H 2混合物中分子氢的低温活化

  摘要：

  分子氢（0.8–8 bar）在0°C下在正己烷中存在2 bar一氧化碳的情况下，与CoRh（CO）7反应，生成HCo（CO）4和Rh 4（CO）12。当CoRh（CO）7（10 -3 mmol / 1）和3,3-二甲基-1-丁烯（0.2 mol / 1）在正己烷中的溶液在2巴一氧化碳和8巴氢气下于0 ℃，观察到4，4-二甲基戊醛的催化形成（24小时后25％的转化率）。尽管分子氢活化的反应路径尚不清楚，但会形成未观察到的中间体（例如H 2 CoRh（CO）7），然后将其裂解生成HCo（CO）4似乎很可能出现非常不稳定的氢铑物种，例如HRh（CO）3，迅速产生Rh 4（CO）12。结果表明，即使使用CoRh（CO）7在相当高浓度的一氧化碳存在下，也可以在0°C下实现分子氢的低温活化。

  DOI：

  10.1016/0022-328x(88)87108-0
• 作为产物：
  描述：

  Dirhodium dicobalt dodecacarbonyl 在 一氧化碳 作用下， 以 正己烷 为溶剂， 生成 cobalt-rhodium heptacarbonyl
  参考文献：
  名称：

  钴铑七羰基化合物形成的动力学

  摘要：

  The kinetics of the reaction Co2Rh2(CO)12 + 2CO --> 2CoRh(CO)7 have been studied at T = 267-294 K and at P(CO) = 0.05-0.20 MPa (8.7 x 10(-4)-4.8 x 10(-3) mole fraction) in n-hexane as solvent. The rate of the reaction was found to be first order in the mixed-metal cluster Co2Rh2(CO)12 (1) and to be consistent with the two-term rate expression rate = {k1 + k2[CO]}[Co2Rh2(CO)12], where the term k1[Co2Rh2(CO)12] represents the single most important contribution to the overall rate of cluster fragmentation under the present reaction conditions. The activation parameters determined from 20 experiments are DELTA-H double-ended-dagger 1 = 60.6 +/- 1.9 kJ/mol (14.5 +/- 0.4 kcal/mol), DELTA-S double-ended-dagger 1 = -80.3 +/- 6.7 J/(mol K) (-19.2 +/- 1.6 cal/(mol K)) and DELTA-H double-ended-dagger 2 = 53.3 +/- 6.6 kJ/mol (12.7 +/- 1.6 kcal/mol), DELTA-S double-ended-dagger 2 = -64.4 +/- 23.5 J/(mol K) (-15.4 +/- 5.6 cal/(mol K)). It is proposed that two independent reaction pathways are available for the transformation of Co2Rh2(CO)12 (1) to CoRh(CO)7 (2) and that these are characterized by (I) an intramolecular activation of Co2Rh2(CO)12 and (II) either (a) the bimolecular reaction of Co2Rh2(CO)12 with CO or (b) the unimolecular reaction of a preequilibrated species {Co2Rh2(CO)13}, as the rate-determining steps.

  DOI：

  10.1021/om00054a025

文献信息

• The formation of a new mixed cobalt rhodium carbonyl from Co2(CO)8 and Rh4(CO)12: Infrared spectroscopic characterization under carbon monoxide pressure
  作者：Felix Splinder、György Bor、Urs K. Dietler、Piero Pino

  DOI：10.1016/s0022-328x(00)93967-6

  日期：1981.6

  and 1956 cm-1, has been in the reaction between Co2(CO)8 and Rh4(CO)12 under carbon monoxide pressure in a hydrocarbon medium. The same compound is also formed either by the reaction of Co2(CO)8 with [Rh(CO)2Cl]2 or by the reaction of Co3Rh(CO)12 with carbon monoxide. The new complex has not been isolated in a pure state, but the formula CoRh(CO)7 is proposed on the basis of the stoichiometry of its

  一氧化碳压力下，Co 2（CO）8和Rh 4（CO）12之间的反应形成了一种新化合物，其最典型的红外吸收带出现在2007 cm -1和1956 cm -1处。在碳氢化合物介质中。通过Co 2（CO）8与[Rh（CO）2 Cl] 2的反应，或通过Co 3 Rh（CO）12与一氧化碳的反应，也可以形成相同的化合物。尚未以纯净状态分离出新的配合物，但分子式为CoRh（CO）7根据其形成的化学计量和其理化性质提出了“环糊精”。平衡常数和热动力学参数对于该反应共2 2（CO）8 +的Rh 4（CO）12 4 CoRh（CO）7进行了估计。在新复合物的红外光谱的基础上，讨论了其可能的结构。
• Low temperature activation of molecular hydrogen in Co/H2 mixtures in the presence of CoRh(CO)7
  作者：István T. Horváth、Marc Garland、György Bor、Piero Pino

  DOI：10.1016/0022-328x(88)87108-0

  日期：1988.12

  unobserved intermediate such as H2CoRh(CO)7, and its subsequent fragmentation to give HCo(CO)4 and a very unstable hydridorhodium species such as HRh(CO)3 rapidly yielding Rh4(CO)12 seems likely. The results show that low temperature activation of molecular hydrogen can be achieved at 0°C even in the presence of substantial concentrations of carbon monoxide using CoRh(CO)7.

  分子氢（0.8–8 bar）在0°C下在正己烷中存在2 bar一氧化碳的情况下，与CoRh（CO）7反应，生成HCo（CO）4和Rh 4（CO）12。当CoRh（CO）7（10 -3 mmol / 1）和3,3-二甲基-1-丁烯（0.2 mol / 1）在正己烷中的溶液在2巴一氧化碳和8巴氢气下于0 ℃，观察到4，4-二甲基戊醛的催化形成（24小时后25％的转化率）。尽管分子氢活化的反应路径尚不清楚，但会形成未观察到的中间体（例如H 2 CoRh（CO）7），然后将其裂解生成HCo（CO）4似乎很可能出现非常不稳定的氢铑物种，例如HRh（CO）3，迅速产生Rh 4（CO）12。结果表明，即使使用CoRh（CO）7在相当高浓度的一氧化碳存在下，也可以在0°C下实现分子氢的低温活化。
• Horváth, István T., Organometallics, 1986, vol. 5, # 11, p. 2333 - 2340
  作者：Horváth, István T.

  DOI：——

  日期：——
• Regiospecific reactions of cobalt-rhodium mixed-metal clusters. Unprecedented, facile and reversible tetranuclear-dinuclear transformations involving diphenylacetylene and/or carbon monoxide
  作者：Istvan T. Horvath、Laszlo Zsolnai、Gottfried Huttner

  DOI：10.1021/om00132a034

  日期：1986.1
• Kinetics of the formation of cobalt-rhodium heptacarbonyl
  作者：Marc Garland、Piero Pino

  DOI：10.1021/om00054a025

  日期：1991.8

  The kinetics of the reaction Co2Rh2(CO)12 + 2CO --> 2CoRh(CO)7 have been studied at T = 267-294 K and at P(CO) = 0.05-0.20 MPa (8.7 x 10(-4)-4.8 x 10(-3) mole fraction) in n-hexane as solvent. The rate of the reaction was found to be first order in the mixed-metal cluster Co2Rh2(CO)12 (1) and to be consistent with the two-term rate expression rate = k1 + k2[CO]}[Co2Rh2(CO)12], where the term k1[Co2Rh2(CO)12] represents the single most important contribution to the overall rate of cluster fragmentation under the present reaction conditions. The activation parameters determined from 20 experiments are DELTA-H double-ended-dagger 1 = 60.6 +/- 1.9 kJ/mol (14.5 +/- 0.4 kcal/mol), DELTA-S double-ended-dagger 1 = -80.3 +/- 6.7 J/(mol K) (-19.2 +/- 1.6 cal/(mol K)) and DELTA-H double-ended-dagger 2 = 53.3 +/- 6.6 kJ/mol (12.7 +/- 1.6 kcal/mol), DELTA-S double-ended-dagger 2 = -64.4 +/- 23.5 J/(mol K) (-15.4 +/- 5.6 cal/(mol K)). It is proposed that two independent reaction pathways are available for the transformation of Co2Rh2(CO)12 (1) to CoRh(CO)7 (2) and that these are characterized by (I) an intramolecular activation of Co2Rh2(CO)12 and (II) either (a) the bimolecular reaction of Co2Rh2(CO)12 with CO or (b) the unimolecular reaction of a preequilibrated species Co2Rh2(CO)13}, as the rate-determining steps.