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Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E‐CH 2 ‐E′ Frustrated Lewis Pairs
Author(s) -
CabreraTrujillo Jorge Juan,
Fernández Israel
Publication year - 2018
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.201804198
Subject(s) - geminal , frustrated lewis pair , reactivity (psychology) , lewis acids and bases , chemistry , density functional theory , activation energy , stereochemistry , transition state , decomposition , computational chemistry , crystallography , catalysis , organic chemistry , alternative medicine , pathology , medicine
The influence of the nature of the acid/base pairs on the reactivity of geminal frustrated Lewis pairs (FLPs) (Me 2 E‐CH 2 ‐E′Ph 2 ) has been computationally explored within the density functional theory framework. To this end, the dihydrogen‐activation reaction, one of the most representative processes in the chemistry of FLPs, has been selected. It is found that the activation barrier of this transformation as well as the geometry of the corresponding transition states strongly depend on the nature of the E/E′ atoms (E=Group 15 element, E′=Group 13 element) in the sense that lower barriers are associated with earlier transition states. Our calculations identify the geminal N/Al FLP as the most active system for the activation of dihydrogen. Moreover, the barrier height can be further reduced by replacing the phenyl group attached to the acidic atom by C 6 F 5 or 3,5‐(CF 3 ) 2 C 6 H 3 (Fxyl) groups. The physical factors controlling the computed reactivity trends are quantitatively described in detail by means of the activation strain model of reactivity combined with the energy decomposition analysis method.