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Mechanistic Insights into Hydrogen Activation by Frustrated N/Sn Lewis Pairs
Author(s) -
Das Shubhajit,
Mondal Sukanta,
Pati Swapan K.
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.201705861
Subject(s) - frustrated lewis pair , lewis acids and bases , chemistry , cationic polymerization , intermolecular force , hydrogen bond , reactivity (psychology) , dabco , stereochemistry , electron pair , non covalent interactions , computational chemistry , molecule , catalysis , polymer chemistry , organic chemistry , electron , physics , medicine , alternative medicine , pathology , quantum mechanics
The mechanism of H 2 activation by recently reported N/Sn Lewis pairs is unravelled using the representative i Pr 3 SnOTf/DABCO combination. Computations provide evidence for weak intermolecular associations between Lewis acid and Lewis base (LA/LB) in which the counteranion to cationic LA fragment plays a critical role. Two frustrated Lewis pairs (FLPs) are observed; an unprecedented counteranion‐mediated noncovalent LA/LB association is characterised along with the usual FLP structure. Both the FLPs are shown to be capable of H 2 activation through cooperative electron transfer processes involving the LA/LB centres. Overall, computed results are in good agreement with the experimental findings and account for the observed reactivity. Insights obtained in this study are fundamentally important for the rational design of Sn‐based alternative FLP LAs. The present findings could also provide a general mechanistic framework for H 2 activation by FLPs having an ion pair LA component.