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. (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 d<sup>8</sup> transition-metal complexes of the type {MCl(PH<sub>3</sub>)<sub>2</sub>}<sup>z+</sup> (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<sup>-1</sup>. Β-Hydride elimination as a competing side reaction was found to be kinetically competitive, but thermodynamically disfavored.
Item Type: | Articles |
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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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