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Gas phase acidities of N-substituted amine-boranes

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Abstract

Complexation energies and acidities of 19 primary, secondary and tertiary amine-boranes were investigated using MP2/6-311+G(d,p) and B3LYP/6-311+G(d,p) methods. Gas phase acidities for free amines were also calculated. Acidity values for studied complexes range from 327.3 to 349.1 kcal mol−1 and the most acidic are the ones with direct connection between deprotonation center and a π-system. Results obtained by both computational methods are in good agreement with each other and with known experimental data. Addition of BH3 increases the acidity of amines by 30 to 50 kcal mol−1. This enhancement effect was compared to the respective effect witnessed in phosphine-boranes and traced back to changes of charge delocalization on nitrogen. A question about the structural stability of several deprotonated amine-borane anions in the gas phase was also raised.

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Acknowledgments

This work was supported by the Estonian Science Foundation (Grant No. 8809) and the Estonian Ministry of Education and Research Targeted Financing project No. SF0180120s08. It was also conducted in part under an Integrated Exchange Program ‘PARROT’ co-financed by the Estonian Science Foundation and the French Ministry of Foreign Affairs.

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Authors and Affiliations

  1. Institute of Chemistry, University of Tartu, 14a Ravila St, Tartu, 50411, Estonia

    Aiko Adamson & Peeter Burk

  2. Institut des Sciences Chimiques de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Avenue du Général Leclerc, CS 50837, 11 Allée de Beaulieu, 35708, Rennes Cedex 7, France

    Jean-Claude Guillemin

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  1. Aiko Adamson
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  2. Jean-Claude Guillemin
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  3. Peeter Burk
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Correspondence to Aiko Adamson or Peeter Burk.

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Calculation results for all species including geometries, electronic energies, enthalpies and free energies at default conditions. This material is available free of charge.

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Adamson, A., Guillemin, JC. & Burk, P. Gas phase acidities of N-substituted amine-boranes. J Mol Model 19, 5089–5095 (2013). https://doi.org/10.1007/s00894-013-2001-y

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