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Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H 2 Addition and Kinetic Analysis
Author(s) -
Chernichenko Konstantin,
Kótai Bianka,
Pápai Imre,
Zhivonitko Vladimir,
Nieger Martin,
Leskelä Markku,
Repo Timo
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201410141
Subject(s) - frustrated lewis pair , chemistry , intramolecular force , hydride , lewis acids and bases , kinetic energy , crystallography , nuclear magnetic resonance spectroscopy , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , hydrogen , catalysis , physics , quantum mechanics
Abstract Ansa ‐aminoborane 1 ( ortho ‐TMPC 6 H 4 BH 2 ; TMP=2,2,6,6‐tetramethylpiperid‐1‐yl), a frustrated Lewis pair with the smallest possible Lewis acidic boryl site (BH 2 ), is prepared. Although it is present in quenched forms in solution, and BH 2 represents an acidic site with reduced hydride affinity, 1 reacts with H 2 under mild conditions producing ansa ‐ammonium trihydroborate 2 . The thermodynamic and kinetic features as well as the mechanism of this reaction are studied by variable‐temperature NMR spectroscopy, spin‐saturation transfer experiments, and DFT calculations, which provide comprehensive insight into the nature of 1 .