Thermodynamic studies and hydride transfer reactions from a rhodium complex to BX3 compounds

Michael T. Mock, Robert G. Potter, Donald M. Camaioni, Jun Li, William G. Dougherty, W. Scott Kassel, Brendan Twamley, Daniel L. DuBois

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Abstract

This study examines the use of transition-metal hydride complexes that can be generated by the heterolytic cleavage of H2 gas to form B-H bonds. Specifically, these studies are focused on providing a reliable and quantitative method for determining when hydride transfer from transition-metal hydrides to three-coordinate BX3 (X = OR, SPh, F, H; R = Ph, p-C 6H4OMe, C6F5, tBu, Si(Me)3) compounds will be favorable. This involves both experimental and theoretical determinations of hydride transfer abilities. Thermodynamic hydride donor abilities (ΔG°H-) were determined for HRh(dmpe)2 and HRh(depe)2, where dmpe ) 1,2-bis(dimethylphosphinoethane) and depe ) 1,2-bis(diethylphosphinoethane), on a previously established scale in acetonitrile. This hydride donor ability was used to determine the hydride donor ability of [HBEt3]- on this scale. Isodesmic reactions between [HBEt3]- and selected BX3 compounds to form BEt3 and [HBX3]- were examined computationally to determine their relative hydride affinities. The use of these scales of hydride donor abilities and hydride affinities for transition-metal hydrides and BX3 compounds is illustrated with a few selected reactions relevant to the regeneration of ammonia borane. Our findings indicate that it is possible to form B-H bonds from B-X bonds, and the extent to which BX3 compounds are reduced by transition-metal hydride complexes forming species containing multiple B-H bonds depends on the heterolytic B-X bond energy. An example is the reduction of B(SPh)3 using HRh(dmpe)2 in the presence of triethylamine to form Et 3N-BH3 in high yields.

Original languageEnglish
Pages (from-to)14454-14465
Number of pages12
JournalJournal of the American Chemical Society
Volume131
Issue number40
DOIs
Publication statusPublished - Oct 14 2009

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Mock, M. T., Potter, R. G., Camaioni, D. M., Li, J., Dougherty, W. G., Kassel, W. S., Twamley, B., & DuBois, D. L. (2009). Thermodynamic studies and hydride transfer reactions from a rhodium complex to BX3 compounds. Journal of the American Chemical Society, 131(40), 14454-14465. https://doi.org/10.1021/ja905287q