Boryltrihydroborate: synthesis, structure, and reactivity as a reductant in ionic, organometallic, and radical reactions

J Am Chem Soc. 2010 Aug 25;132(33):11449-51. doi: 10.1021/ja105277u.

Abstract

Reaction of lithium 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaborol-2-ide with borane.THF provides the first boryl-substituted borohydride: lithium [1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaborol-2-yl]trihydroborate. The compound is fully characterized by (11)B, (1)H, and (7)Li NMR spectra and other means, and these data are compared to neutral and anionic benchmark compounds. The compound crystallizes as a dimer complexed to four THF molecules. The dimer lacks the bridging B-H bonds seen in neutral boranes and is instead held together by ionic Li---HB interactions. A preliminary scan of reactions with several iodides shows that the compound participates in an ionic reduction (with a primary-alkyl iodide), an organometallic reduction (Pd-catalyzed with an aryl iodide), and a radical reduction (AIBN-initiated with a sugar-derived iodide). Accordingly the new borylborohydride class may share properties of both traditional borohydrides and isoelectronic N-heterocyclic carbene boranes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Borates / chemical synthesis*
  • Borates / chemistry*
  • Crystallography, X-Ray
  • Free Radicals / chemistry
  • Ions / chemistry
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Oxidation-Reduction
  • Stereoisomerism

Substances

  • Borates
  • Free Radicals
  • Ions
  • Organometallic Compounds