yield of aldehyde in the absence of phosphines, the yield is increased to 54% in the presence of phosphinated silica P-SiO2} or even 94% if PPh3 is added to the solution. Without extra added phosphine, both 1a and 2a effect mainly the isomerization of 1-hexene to 2-hexene. Pre-catalyst 1a catalyzes also the hydrogenation of benzene at 10.5 atm H2 and 90 °C to give cyclohexane with a TOF of 608 h−1.
在将
铑络合物[Rh(acac)(CO)(P)](1)和[Rh(acac)(P)2 ](2)(P = Ph 2 PCH 2 CH 2 Si(OMe)3)固定化时发现SiO 2,
乙酰丙酮通过酸性
二氧化硅-OH基团使acac
配体质子化而释放。所得络合物[Rh(O- SiO 2 }(HO- SiO 2 })(CO)(P- SiO 2 })](1a)和[Rh(O- SiO 2 })(HO- SiO 2 })(P- SiO 2 })2 ](2a)已成功测试了它们对
1-己烯加氢甲酰化以及苯和
甲苯加氢的催化作用。反应结果,即。醛的形成与异构化的关系在很大程度上取决于膦助催化剂的存在和浓度。因此,尽管在不存在膦的情况下1a仅产生17%的醛收率,但是在存在膦化
二氧化硅P- SiO 2 }的情况下收率增加到54%,或者如果将PPh 3添加到溶液中则收率增加到94%。在没有额外添加膦的情况下,1a