Toward an alkene hydroamination catalyst: Static and dynamic ab initio DFTstudies

The catalytic hydroamination of alkenes via alkene activation and subsequen t nucleophilic attack has been investigated with Car-Parrinello ab initio m olecular-dynamics calculations using the projector-augmented wave method. T he complete cycle including all intermediates and transition stales was stu died with d(8) transition-metal complexes of the type {MCl(PH3)(2)}(z+) (M = Co, Ph, Ir [z = 0] and Ni, Pd, Pt [z = 1] as catalysts, comparing the dif ferent metals for their suitability. For group 9, nucleophilic attack was i dentified as the rate-determining step, while the cleavage of the M-C bond is rate-determining for group 10. Overall, group 10 is more favorable than group 9. In particular, nickel complexes were found to be the best-suited p otential catalysts with an activation barrier for the rate-determining step of 108 kJ mol(-1). beta-Hydride elimination as a competing side reaction w as found to be kinetically competitive, but thermodynamically disfavored.