Structure-Reactivity Relationship in the Frustrated Lewis Pair (FLP)-Catalyzed Hydrogenation of Imines.

The autoinduced, frustrated Lewis pair (FLP)-catalyzed hydrogenation of 16-benzene-ring substituted N-benzylidene-tert-butylamines with B(2,6-F2 C6 H3 )3 and molecular hydrogen was investigated by kinetic analysis. The pKa values for imines and for the corresponding amines were determined by quantum-mechanical methods and provided a direct proportional relationship. The correlation of the two rate constants k1 (simple catalytic cycle) and k2 (autoinduced catalytic cycle) with pKa difference between imine and amine pairs (ΔpKa ) or Hammett's σ parameter served as useful parameters to establish a structure-reactivity relationship for the FLP-catalyzed hydrogenation of imines.