title: Intramolecular frustrated Lewis pair with the smallest boryl site: reversible H2 addition and kinetic analysis.
abstract: Ansa-aminoborane 1 (ortho-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, 1 reacts with H2 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.
authors.affiliation: Department of Chemistry, Laboratory of Inorganic Chemistry, University of Helsinki, A. I. Virtasen aukio 1, 00014 Helsinki (Finland).
authors.forename: Konstantin
authors.initials: K
authors.lastname: Chernichenko
authors.forename: Bianka
authors.initials: B
authors.lastname: Kótai
authors.forename: Imre
authors.initials: I
authors.lastname: Pápai
authors.forename: Vladimir
authors.initials: V
authors.lastname: Zhivonitko
authors.forename: Martin
authors.initials: M
authors.lastname: Nieger
authors.forename: Markku
authors.initials: M
authors.lastname: Leskelä
authors.forename: Timo
authors.initials: T
authors.lastname: Repo
keywords: aminoboranes; density functional calculations; frustrated Lewis pairs; kinetics; thermodynamics