ABSTRACT
Modem electronic structure methodology offers a highly powerful approach to the detailed understanding of many aspects concerning the structure and reactivity of organometallic systems. Given the dearth of high-quality thermodynamic data available for organometallic reactions, the ability to extract energy parameters from electronic structure calculations may arguably be their greatest asset. Thus, reliable and accurate prediction of reaction and activation energies can provide potentially valuable guidance in determining the factors that control the rates and thermodynamics of organometallic reaction mechanisms, including those rele vant to catalysis (1,2). Rational catalyst design and optimization on the basis of electronic structure calculations is within reach (3). High-level computational methods, which are widely applicable to a large variety of problem situations, are in strong demand, and there is a continuous need to evaluate new procedures
and extend old ones. Organometallic chemistry provides a particularly diverse and fruitful field for such endeavors. Procedures such as effective core potentials, now well established in chemistry, have found some of their most impressive applications here (4), and many of the recent advances in density functional the ory have had particular impact in organometallic chemistry (5).
