Homogeneous catalytic kinetics organometallic catalysis

Organometallic chemistry is interesting in part because it has applications to catalytic processes. Since the discovery of C-H bond activation and the homogeneous hydrogenation of olefins, the importance of organometallic complexes has been undisputed. Many experimental smdies of organometallic catalysis have focused on catalyst and substrate structure, kinetics of transformations, mechanisms, thermochemical properties, turnover, selectivity, etc., and a massive quantity of experimental data has been accumulated. Molecular mechanics can be used to compile and analyze these data in order to direct the design of novel catalytic systems. 

Organometallic catalysis is very diverse and many different mechanisms have been proposed in the literature for various reactions. Interestingly it is rather seldom that kinetic models are derived for the proposed catalytic cycles and the kinetic equations are even compared qualitatively with experimental observations. We will discuss several examples which represent typical cases in homogeneous catalysis by metall complexes. 

In this chapter we discuss some of the basic concepts of organometallic chemistry and reaction kinetics that are of special relevance to homogeneous catalysis. The catalytic activity of a metal complex is influenced by the characteristics of the central metal ions and the attached ligands. We first discuss the relevant properties of the metal ion and then the properties of a few typical ligands. 

With growing data banks of rate constants of elementary steps, it appears that kinetics assisted design of new catalytic processes will accelerate the development of improved catalytic processes. With powerful computational methods of thermodynamic and kinetic parameters, microkinetic analysis has emerged as a mature method to describe existing processes in combustion, polymerization, homogeneous and heterogeneous catalysis. In catalysis, the method is now poised to become one of the tools of catalyst development with the help of surface science, organometallic chemistry, materials science, com-... 

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