金属有机化学第九章.pptVIP

* 1. Cobalt-Based Hydroformylation Catalysts Hydroformylation or the oxo process was originally developed by Roelen in the late 1930’s. The original catalyst was Co2(CO)8, which is still widely used. In the hydroformylation reaction, the elements of formaldehyde (H and CHO) are added across a double bond to give an aldehyde. Both linear and branched products can be produced, although the more desirable linear aldehydes are usually the major products when using aliphatic olefins. Depending on the catalyst and conditions, the aldehydes can be directly reduced to alcohols during the reaction. Chapter 9 Hydroformylation and Related Alkene Carbonylations Catalytic cycle: Although the exact nature of some steps have not been conclusively determined, the catalytic cycle is as follows. The mechanism of the hydrogenolysis step is less clear. One possible mechanism is the reaction with H2 to give the aldehyde and HCo(CO)4, which could occur by oxidative addition/reductive elimination (unlikely due to the expected high activation barrier) or heterolytic H2 activation (?-bond metathesis). A second possible mechanism would involve a dinuclear reaction with HCo(CO)4. Evidence for both mechanisms has been observed. HCo(CO)4 reacts 20-30 X faster with the Co-acyl than H2 does at room temperature (Organometallics, 1986, 5, 209-215). Under the catalytic conditions, the H2 concentration is about 2 orders of magnitude larger than that of HCo(CO)4. Regioselectivity: Generally the linear isomer is more valuable industrially than the branched isomer. Since the catalytic cycle is irreversible, the observed regioselectivity represents the kinetic product ratio rather than the thermodynamic preference. The regioselectivity can be modified by adding phosphine to the Co-catalyzed hydroformylation system. This advance was discovered at Shell chemical. Using HCo(CO)3PBu3 as catalyst, higher linear:branched ratios are achieved. This appears to be due to a greater degree of regiocontrol in the in