Ab Initio Energy Calculations and Macroscopic Rate Modeling of Hydroformylation of Higher Alkenes by Rh-Based Catalyst

Ab initio quantum chemical computations have been done to determine the energetics
and reaction pathways of hydroformylation of higher alkenes using a rhodium
complex homogeneous catalyst. Calculation of fragments of the potential energy surfaces
of the HRh(CO)(PPh3)3-catalyzed hydroformylation of 1-decene, 1-dodecene, and
styrene were performed by the restricted Hartree-Fock method at the second-order
MØller-Plesset (MP2) level of perturbation theory and basis set of 6-31þþG(d,p).
Geometrically optimized structures of the intermediates and transition states were
identified. Three generalized rate models were developed on the basis of above
reaction path analysis as well as experimental findings reported in the literature. The
kinetic and equilibrium parameters of the models were estimated by nonlinear least
square regression of available literature data. The model based on H2-oxidative addition
fitted the data best; it predicts the conversion of all the alkenes quite satisfactorily
with an average deviation of 7.6% and a maximum deviation of 13%.