Using correlations to compare additions to alkenes: homogeneous hydrogenation by using Wilkinson's catalyst.

Plots of the logarithms of relative rates of homogeneous catalytic hydrogenation of alkenes (log k(rel) values) by using Wilkinson's catalyst versus their ionization potentials (IPs) and versus their lowest unoccupied molecular orbital energy levels (LUMOs) display good-to-excellent correlations. The correlations indicate that the rate-determining step of this reaction is a nucleophilic addition to the alkene double bond, which is dependent upon both electronic effects and steric effects. This conclusion is in agreement with only two of three previously proposed mechanisms for the reaction, effectively ruling out one in which the rate-determining step involves electrophilic addition to the alkene. Characteristics of the analysis using these correlations are compared and contrasted with other additions to alkenes, such as the Wacker oxidation, to probe patterns in transition state characteristics.