Computational Study of the Ene/Rearrangement Reaction between (F<sub>3</sub>C)<sub>2</sub>BNMe<sub>2</sub>, <b>1</b>, and Acetonitrile: Reactant-Catalyzed Mechanism of the Ketenimine–Nitrile-Like Rearrangement Sherdenia V. Barbary Timothy R. Bryan Thomas M. Gilbert 10.1021/acs.jpca.9b09403.s001 https://acs.figshare.com/articles/journal_contribution/Computational_Study_of_the_Ene_Rearrangement_Reaction_between_F_sub_3_sub_C_sub_2_sub_B_NMe_sub_2_sub_b_1_b_and_Acetonitrile_Reactant-Catalyzed_Mechanism_of_the_Ketenimine_Nitrile-Like_Rearrangement/10005467 The reaction between (F<sub>3</sub>C)<sub>2</sub>BNMe<sub>2</sub>, <b>1</b>, and acetonitrile at low temperature in pentane yields a bora-acetonitrile rather than the expected coordination complex. This appears to arise from the two undergoing an ene reaction followed by a rearrangement analogous to a ketenimine–nitrile rearrangement. Computational studies indicate that mechanistic steps suggested for the latter require energies too large for the reaction to take place under the experimental conditions. Instead, a mechanism in which the ene reaction product is attacked by a second molecule of <b>1</b>, followed by hydrogen transfer and decomposition, exhibits barriers lower than that for the ene reaction. The mechanism implies that the fragment of <b>1</b> in the observed product is not the one that underwent the ene reaction. The ene reaction barrier is rate-determining, and it is low enough to conform to the experimental conditions. 2019-10-18 21:29:26 ene reaction product ene reaction ene reaction barrier F 3 C