金属有机化学第八章.pptVIP

* Alkene hydrogenation is one of the oldest metal catalyzed reactions (Pd/C) and one of the first homogeneous catalytic cycles to be carefully studied mechanistically. There are three steps involved in nearly all hydrogenation reactions. 1) Hydrogen activation: oxidative addition (concerted mechanism), heterolytic, or homolytic 2) Migratory insertion 3) Elimination of alkane: Reductive elimination, ?-bond metathesis or homolytically Chapter 8 Catalytic Hydrogenation Wilkinsons Catalyst: RhCl(PPh)3 The rate of hydrogenation of alkenes by Wilkinsons catalyst mirror their relative binding affinity to the metal center. Differences in rate between the alkenes is about 50X. Alkenes that bind tightly (i.e. ethylene) give slow hydrogenation rates, though. Proposed mechanism as elucidated by Halpern: (J. Mol. Cat. 1976, 2, 65; J. Am. Chem. Soc. 1977, 99, 8055; J. Am. Chem. Soc., 1980, 102, 838; Science, 1982, 217, 401) The hydrogenation reaction occurs in two steps: 1) Dihydrogen activation 2) Alkene hydrogenation Since H2 is activated first, this is often called the hydride path. Dihydrogen activation: Halperns evidence supports an initial dissociation of PPh3 prior to oxidative addition of H2. The rate of oxidative addition is inhibited by increased [PPh3]. In fact the direct addition of H2 to 1 to give 3 in the presence of excess PPh3 occurs very slowly. (J. Mol. Cat. 1976, 2, 65. Inorg. Chim. Act. 1981, 50, 11). Oxidative addition of H2 was estimated by Halpern to occur 104 X faster, which was later confirmed by generating 2 by flash photolysis. (J. Am. Chem. Soc. 1985, 107, 1794. and 1986, 108, 4838). Very slowly 2 has a strong tendency to dimerize to 8, although this is not a significant process under higher H2 pressures. The alkene complex 7 also does not represent a significant trap for the Rh species, except in the case of tightly binding alkenes such as ethylene. Olefin Hydrogenation: Kinetic studies were carried out on the reaction of 3 with a large e