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应 用 原 位 红 外 光 谱 技 术, 研 究 了 Rh ( acac) ( C O) ( P Ph3) 、 H Rh ( C O) ( P Ph3) 3 、 Rh 6 ( C O) 16 和( Rh( C H3 C O O) 2)24 种催化剂,在 C O/ H2 气氛中催化1辛烯氢甲酰化 反应时 Rh 催化剂的活 化过程。结果表明,在以 O P Ph3 为配体的情况下,催化剂的中间体均为 Wilkinson 型配合物 H Rh( C O)x( O P Ph3) y( x + y = 3 或4) ,此外,同时还存在有二聚体、多羰基铑配合物等。当4 种催化剂在无配体的情况下,醛化反应的活性仍然较高,此时观察到在使用( Rh( C H3 C O O) 2) 2 及 Rh 6( C O)16 时, 最终生 成 H Rh( C O)4 的活性中 间体。当使 用 R H(acac) ( C O) ( P Ph3) 及 H Rh( C O)( P Ph3) 3 时,活性中间体仍然以 H Rh( C O)x( P Ph3) y 型配合物为主,同时可能存在少量的 H Rh( C O) 4 中间物。
The effects of Rh (acac) (C O) (P Ph3), H Rh (C 0) (P Ph3) 3, Rh 6 (C O) 16 and Rh (C H3 C O O ) 2) 24 kinds of catalysts, catalytic activity of Rh catalyst in 1-octene hydroformylation reaction in C O / H 2 atmosphere. The results show that the catalyst intermediates are both the Wilkinson type complexes H Rh (C O) x (O P Ph3) y (x + y = 3 or 4) in the case of O P Ph3 as the ligand. In addition, There are also dimers, polycarbonyl rhodium complexes and the like. The hydroformylation reaction activity was still high when the four catalysts were in the absence of a ligand, when the final (Rh (C H3 C O O) 2) 2 and Rh 6 (C 0) 16 were observed The active intermediate of H Rh (C 0) 4 is generated. The active intermediates are still in the form of an H Rh (C 0) x (P Ph3) y type complex when R H (acac) (C 0) (P Ph3) and H Rh (C 0) (P Ph3) At the same time, there may be a small amount of H Rh (Co) 4 intermediate.