Dirhodium dicobalt dodecacarbonyl | 12560-37-1

• 分子结构分类: 无机化合物
• 英文名称: Dirhodium dicobalt dodecacarbonyl
• 英文别名: carbon monoxide;cobalt;rhodium
• CAS: 12560-37-1
• 化学式: C₁₂Co₂O₁₂Rh₂
• 分子量: 659.922
• InChiKey: FVLDHZOROGRFRS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.46
• 重原子数：
  28
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  sodium tetracarbonyl cobaltate 、 di(rhodium)tetracarbonyl dichloride 在 CO 作用下， 以 正己烷 为溶剂， 以99%的产率得到Dirhodium dicobalt dodecacarbonyl
  参考文献：
  名称：

  七羰基钴铑：配位不饱和的二核金属羰基

  摘要：

  DOI：

  10.1021/om00138a024

文献信息

• Ligand substitution in [CoxRh4−x(CO)12] (x = 3 or 2) with tertiary phosphines or phosphites, including the X-ray structure of [Co2Rh2(CO)11(PPh3)]
  作者：Maria Bojczuk、Brian T. Heaton、S. Johnson、Carlo A. Ghilardi、Annabella Orlandini

  DOI：10.1016/0022-328x(88)89101-0

  日期：1988.3

  Ligand substitution of the mixed-metal clusters [Co3Rh(CO)12] and [Co2Rh2(CO)12] with triphenylphosphine or triphenylphosphite has been studied by NMR spectrometry and shown to occur preferentially at the rhodium centres. The molecular structure of [Co2Rh2(CO)11(PPh3)] has been determined by X-ray crystallography, and shown to be related to that of the parent cluster: both rhodium atoms are in the

  已经通过NMR光谱法研究了三苯膦或亚磷酸三苯酯对混合金属簇[Co 3 Rh（CO）12 ]和[Co 2 Rh 2（CO）12 ]的配体取代，并显示优先出现在铑中心。[Co 2 Rh 2（CO）11（PPh 3）]的分子结构已通过X射线晶体学测定，并显示出与母体簇的结构相关：两个铑原子都在基面上，三苯基膦在轴向位点连接到铑。
• On the mechanism of silylformylation catalyzed by Rh-Co mixed metal complexes
  作者：Iwao Ojima、Li Zhaoyang、Robert J. Donovan、Patrizia Ingallina

  DOI：10.1016/s0020-1693(97)05855-6

  日期：1998.4

  1-alkynes catalyzed by Rh2Co2(CO)12 are investigated. Novel Rh-Co mixed metal complexes, (PhMe2Si)2Rh(CO)nCo(CO)4 (n = 2 or 3) (3) and RhCo(HC≡CBun)(CO)5 (5), are found to play important roles in this catalysis. The reaction of 3 with 1-hexyne and HSiMe2Ph at ambient temperature and pressure of CO gives n-BuC(CHO)=CHSiMe2Ph (1a, Z/E = 95/5), (PhMe2Si)2Rh(CO)3Co(CO)4 (3-B) and an Rh-Co mixed metal butterfly

  研究了Rh2Co2（CO）12催化1-炔烃的甲硅烷基甲酰化的可能机理。发现新型Rh-Co混合金属络合物（PhMe2Si）2Rh（CO）nCo（CO）4（n = 2或3）（3）和RhCo（HC≡CBun）（CO）5（5）具有重要作用在这种催化中的作用。3在环境温度和CO压力下与1-己炔和HSiMe2Ph的反应得到n-BuC（CHO）= CHSiMe2Ph（1a，Z / E = 95/5），（PhMe2Si）2Rh（CO）3Co（CO）4 （3-B）和Rh-Co混合金属蝴蝶络合物h2Co2（HC≡CBun）（CO）10（4）。在相同的环境条件下5与1-己炔和HSiMe2Ph的反应非常干净地提供1a（100％Z）作为唯一的反应产物。使用RhCo（DC≡CBun）（CO）5（5-d），1-己炔-1d和DSiMe2Ph进行的交叉实验有力地支持了混合金属双金属催化和双（炔）-Rh-Co物种的参与。
• Horváth, István T., Organometallics, 1986, vol. 5, # 11, p. 2333 - 2340
  作者：Horváth, István T.

  DOI：——

  日期：——
• Bahsoun; Osborn; Voelker, Organometallics, 1982, vol. 1, # 9, p. 1114 - 1120
  作者：Bahsoun、Osborn、Voelker、Bonnet、Lavigne

  DOI：——

  日期：——
• Heterosite reactivity of cobalt-rhodium mixed- metal clusters
  作者：Istvan T. Horvath

  DOI：10.1016/s0277-5387(00)86352-4

  日期：1988.1