Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H-2 Addition and Kinetic Analysis

Chernichenko, K. and Kótai, Bianka and Pápai, Imre and Zhivonitko, V. and Nieger, M. (2015) Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H-2 Addition and Kinetic Analysis. ANGEWANDTE CHEMIE INTERNATIONAL EDITION, 54 (6). pp. 1749-1753. ISSN 1433-7851

Text Chernichenko_et_al_2015_u.pdf Restricted to Repository staff only Download (806kB) | Request a copy

Abstract

Ansa-aminoborane 1 (ortho-TMPC6H4BH2; TMP=2,2,6,6-tetramethylpiperid-1-yl), a frustrated Lewis pair with the smallest possible Lewis acidic boryl site (BH2), is prepared. Although it is present in quenched forms in solution, and BH2 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.

Actions (login required)

Edit Item