Bicyclic phosphines as ligands for cobalt catalysed hydroformylation. Crystal structures of [Co(Phoban[3.3.1]-Q)(CO)3]2 (Q = C2H5, C5H11, C3H6NMe2, C6H11)
作者:Peter N. Bungu、Stefanus Otto
DOI:10.1039/b702709e
日期:——
higher yields due to less hydrogenation of the olefin. In comparison, at fully modified conditions, PBu3 gave a rate of 0.6 h−1, alcohol yield of 77%, linearity of 81% and 17% hydrogenation. The crystal structures of the cobalt dimers [Co(CO)3(Phoban[3.3.1]-C2)]2, [Co(CO)3(Phoban[3.3.1]-C5)]2, [Co(CO)3(Phoban[3.3.1]-C3NMe2)]2, and [Co(CO)3(Phoban[3.3.1]-Cy)]2 have been determined and indicated very similar
一系列叔双环膦 配体源自顺式,顺-1,5-环辛二烯(Phoban家族)是通过使用钴催化剂体系在线性内部混合物的加氢甲酰化过程中通过分批高压釜反应进行研究的。用PBu 3作为标准三烷基膦行为的代表进行比较试验。普班配体由环辛基自行车和[3.3.1]和[4.2.1]异构体的混合物组成,其中第三个取代基有系统地变化,Phoban-Q(Q = CH 2 CH 3,(CH 2)4 CH 3,( CH 2)9 CH 3,(CH 2)19 CH 3,(CH 2)3 N(CH 3)2,C 6 H 11和C 6 H 5)。增加配体 随着从更未改性的催化作用向更改性的催化作用的转变,浓度降低导致反应速率降低,而对正醇产物的选择性增加。 酒精对于高度修饰的催化,在1.8–2.4 h -1的速率下可获得77–85%的产率。在高度修改的条件下,酒精 从Phoban-Ph到Phoban-Cy的狭窄范围分别为〜85–90%。