Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H2 Addition and Kinetic Analysis1. Issue 6 (17th December 2014)

• Record Type: Journal Article
• Authors: Chernichenko, Konstantin; Kótai, Bianka; Pápai, Imre; Zhivonitko, Vladimir; Nieger, Martin; Leskelä, Markku; Repo, Timo
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 6(2015)
• Page Start: 1749
• Page End: 1753
• Publication Date: 2014-12-17
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201410141
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p> <italic>Ansa</italic>‐aminoborane <bold>1</bold> (<italic>ortho</italic>‐TMPC₆H₄BH₂; 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, <bold>1</bold> reacts with H₂ under mild conditions producing <italic>ansa</italic>‐ammonium trihydroborate <bold>2</bold>. 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 <bold>1</bold>.</p> </abstract>