Study of the competitive mechanisms of cyclohexane dehydrogenation by gas-phase Ni2(+) cationic dimer: one-face dehydrogenation versus flip dehydrogenation.

The mechanism of cyclohexane dehydrogenation catalyzed by the cationic dimer Ni2 (+) has been investigated at the B3LYP level of density functional theory. The first dehydrogenation occurs readily (it is exothermic by 30 kcal/mol), whereas the second and third dehydrogenations show weaker exothermicity than the first (23 and 21 kcal/mol, respectively). These three hydrogenations corresponding to the total dehydrogenation of one face of cyclohexane mainly proceed in the doublet state due to the presence of significant minimum-energy crossing points (MECPs).