CH3Co(CO)3PPh3 | 583058-08-6

• 英文名称: CH3Co(CO)3PPh3
• CAS: 583058-08-6
• 化学式: C₂₂H₁₈CoO₃P
• 分子量: 420.35
• InChiKey: DGWUNTBDONKAOB-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [(acetyl)(triphenylphosphine)Co(CO)3] 以 苯 为溶剂， 生成 CH3Co(CO)3PPh3
  参考文献：
  名称：

  与基于羰基钴的羰基化催化剂有关的反应性中间体的活化参数。

  摘要：

  时间分辨光谱技术已被用于制备和询问瞬态物质，这些物质是钴催化加氢甲酰化反应中反应中间体的模型。RC（O）Co（CO）3（PR'3）型（A； R = CH3，CD3或C2H5； R'= Ph或nBu）的乙酰钴羰基配合物的快速光解导致CO光解，得到“不饱和”中间体[RC（O）Co（CO）2（PR'3）]（I），它通过两种竞争途径衰减，烷基迁移至钴，得到RCo（CO）3PR'3（M），并与CO重整为A。使用全氘乙酰基复合物（R = CD3，R'= Ph），CO捕集（kco）和甲基迁移（kM）的速率常数都略小于perprotio类似物（kh / kd分别为1.04 +/- 0.01和1.07 +/- 0.09）。因此，“

  DOI：

  10.1021/ic020567b

文献信息

• Time-Resolved Infrared Spectroscopic Study of Reactive Acyl Intermediates Relevant to Cobalt-Catalyzed Carbonylations¹
  作者：Steven M. Massick、Julienne G. Rabor、Stefan Elbers、Jon Marhenke、Stefan Bernhard、Jon R. Schoonover、Peter C. Ford

  DOI：10.1021/ic000378y

  日期：2000.7.1

  Time-resolved infrared spectroscopic studies have been used to characterize the reactive intermediate CH3C(O)Co(CO)(2)-PPh3 (I-Co), which is relevant to the mechanism of the catalysis of alkene hydroformylation by the phosphine-modified cobalt carbonyls. Step-scan FTIR and (variable) single-frequency time-resolved infrared detection on the microsecond time scale were used to record the spectrum of I-Co and to demonstrate that the principal photoproduct of the subsequent reaction of this species at P-CO = 1 atm is the methyl cobalt complex CH3Co-(CO)(3)PPh3 (M-Co). At higher P-CO the trapping of I-Co with CO to re-form CH3C(O)Co(CO)(3)PPh3 (A(Co)) (rate = k(CO)[CO][I-Co]) was shown to become competitive with the rate of acetyl-to-cobalt methyl migration to give M-Co (rate = k(M)[I-Co]) Activation parameters for the competing pathways in benzene were determined to be Delta H-CO(double dagger) = 5.7 +/- 0.4 kJ mol(-1), Delta S-CO(double dagger) = -91 +/- 12 J mol(-1) K-1 and Delta H-M(double dagger) = 40 +/- 2 kJ mol(-1), Delta S-M(double dagger) = -19 +/- 5 J mol(-1) K-1. The effects of varying the solvent on the competitive reactions of I-Co were also explored, and the mechanistic implications of these results are discussed.