The DFT study on CC activation of butanone by Ni+ in gas phase: Two parallel decomposition reaction mechanisms

The different potential energy surfaces (PESs) of Ni+ (2D, 3d9) with butanone in gas phase have been systematically explored by density functional theory (DFT). Two parallel decomposition reaction mechanisms have been identified. The course that the Ni+ inserts into the σ-bond of the CC2H5 or CCH3 leading to the CC bond activation has been analyzed using the natural bond orbital (NBO). Finally, the conclusion of the theory calculation was consistent with the experimental results which provided by the Darrin J. Bellert group in 2011 that three neutral organic molecule products (ethylene, acetaldehyde and methane) were obtained.

Graphical abstractThese diagrams for the two parallel decomposition reaction PESs of the reaction Ni+/butanone in the doublet and quartet states.Download full-size imageHighlights► Reactants, intermediates and transition states are calculated. ► The natural bond orbital of two CC activations have been analyzed. ► Two parallel decomposition reaction mechanisms have been discussed. ► The crucial activation barriers of two elementary steps have been discussed.