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Structure–Reactivity Relationship in the Frustrated Lewis Pair (FLP)‐Catalyzed Hydrogenation of Imines
Author(s) -
Tussing Sebastian,
Kaupmees Karl,
Paradies Jan
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600716
Subject(s) - frustrated lewis pair , reactivity (psychology) , catalysis , chemistry , materials science , lewis acids and bases , organic chemistry , medicine , alternative medicine , pathology
Abstract The autoinduced, frustrated Lewis pair (FLP)‐catalyzed hydrogenation of 16‐benzene‐ring substituted N ‐benzylidene‐ tert ‐butylamines with B(2,6‐F 2 C 6 H 3 ) 3 and molecular hydrogen was investigated by kinetic analysis. The p K a 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 k 1 (simple catalytic cycle) and k 2 (autoinduced catalytic cycle) with p K a difference between imine and amine pairs (Δp K a ) or Hammett's σ parameter served as useful parameters to establish a structure–reactivity relationship for the FLP‐catalyzed hydrogenation of imines.