金属有机化学第十二章.pptVIP

* Chapter 12 Alkene Metathesis Alkene metathesis is the metal-catalyzed disproportion of alkenes. This reaction has been known for nearly 50 years, but only in the past decade has it become widely used in both industrial and academic labs for the synthesis of polymers and complex organic compounds. The 2005 Nobel prize was award to Yves Chauvin, Richard Schrock, and Robert Grubbs for their work in developing olefin metathesis into a widely used process. There are several classes of olefin metathesis reactions. All of the above reactions are reversible, so equilibrium mixtures are obtained. To produce high yields of a given product a suitable driving force must be present. ? Cross metathesis: Mixtures of products are produced unless a volatile byproduct (ethylene) is produced that can be removed from the reaction mixture. ? RCM is favored for the production of unstrained rings and is driven both entropically and by the elimination of a volatile alkene. ? ROM is only favored at very high olefin concentrations, or more commonly with strained olefins. Olefin metathesis was discovered in the 1950’s about the same time as Ziegler-Natta olefin polymerization. The catalysts used from this time through the 80’s were poorly defined combinations of a metal salt and main-group organometallic species. (i.e., WCl5/Bu4Sn or MoCl2(NO)2(PPh3)2/Al2Me3Cl3. These types of catalysts are still used industrially. Metathesis in the Shell Higher Olefin Process (SHOP) cat Mechanism: The mechanism of the reaction was disputed for a long time. One of the early proposals by Chauvin turned out to be correct, but was not accepted for some time. His early contribution was the reason he was awarded the Nobel prize. J. Am. Chem. Soc., 1976, 98, 2519 Well-defined catalysts With the acceptance of the Chauvin mechanism, metal-carbene complexes were explored for their ability to catalyze olefin metathesis. The first active, well-defined system was (OC)5W=CPh2 (Tetr. Lett., 1976, 17, 4247).