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Toward an alkene hydroamination catalyst: static and dynamic ab initio DFT studies

Senn, H.M., Blöchl, P.E., and Togni, A. (2000) Toward an alkene hydroamination catalyst: static and dynamic ab initio DFT studies. Journal of the American Chemical Society, 122 (17). pp. 4098-4107. ISSN 0002-7863 (doi:10.1021/ja992689h)

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Publisher's URL: http://dx.doi.org/10.1021/ja992689h

Abstract

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 d8 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.

Item Type:Article
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Senn, Dr Hans
Authors: Senn, H.M., Blöchl, P.E., and Togni, A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1943-2984

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