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Intramolecular frustrated Lewis pair with the smallest boryl site: reversible H2 addition and kinetic analysis
Konstantin Chernichenko1, Bianka Kótai, Imre Pápai
1Department of Chemistry, Laboratory of Inorganic Chemistry, University of Helsinki, A. I. Virtasen aukio 1, 00014 Helsinki (Finland).
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.
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