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New Insights in Frustrated Lewis Pair Chemistry with Azides
Author(s) -
Boom Devin H. A.,
Jupp Andrew R.,
Nieger Martin,
Ehlers Andreas W.,
Slootweg J. Chris
Publication year - 2019
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.201902710
Subject(s) - frustrated lewis pair , chemistry , geminal , steric effects , adduct , lewis acids and bases , reactivity (psychology) , ring (chemistry) , medicinal chemistry , azide , hydrazoic acid , electron pair , disiloxane , silylene , stereochemistry , organic chemistry , catalysis , silicon , electron , medicine , physics , alternative medicine , pathology , quantum mechanics
The geminal frustrated Lewis pair (FLP) t Bu 2 PCH 2 BPh 2 ( 1 ) reacts with phenyl‐, mesityl‐, and tert ‐butyl azide affording, respectively, six, five, and four‐membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six‐membered ring structure, which is thermally stable with an N‐phenyl group, but rearranges when sterically more encumbered Mes−N 3 and t Bu−N 3 are used. The reaction of 1 with Me 3 Si−N 3 is believed to follow the same course, yet subsequent N 2 elimination occurs to afford a four‐membered heterocycle ( 5 ), which can be considered as a formal FLP‐trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.