Karlheinz Schwarz, Ernst Nusterer, et al.
Catalysis Today
The catalytic hydroamination of alkenes via alkene activation and subsequent nucleophilic attack has been investigated with Car-Parrinello ab initio molecular-dynamics calculations using the projector-augmented wave method. The complete cycle including all intermediates and transition states was studied with ds transition-metal complexes of the type {MCl(PH3)2}(z+) (M = Co, Rh, Ir [z = 0] and Ni, Pd, Pt [z = 1]) as catalysts, comparing the different metals for their suitability. For group 9, nucleophilic attack was identified 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 potential catalysts with an activation barrier for the rate-determining step of 108 kJ mol-1. β-Hydride elimination as a competing side reaction was found to be kinetically competitive, but thermodynamically disfavored.
Karlheinz Schwarz, Ernst Nusterer, et al.
Catalysis Today
Ernst Nusterer, Peter E. Blöchl, et al.
Angewandte Chemie (International Edition in English)
Reinhard Nesper, Karlheinz Vogel, et al.
Angewandte Chemie International Edition in English
Peter E. Blöchl, James H. Stathis
Physical Review Letters