Teaching an Old Reagent New Tricks: Synthesis, Unusual Reactivity, and Solution Dynamics of Borohydride Grignard Compounds

Joseph Reynolds III, Austin Acosta, ShinYoung Kang, Sichi Li, Andrew Lipton, Mark Bowden, Nicholas Myllenbeck, Andreas Schneemann, Noemi Leick, Austin Bhandarkar, Christopher Reed, Robert Horton, Thomas Gennett, Brandon Wood, Mark Allendorf, Vitalie Stavila

Research output: Contribution to journalArticlepeer-review

1 Scopus Citations


Grignard reagents of the general formula RMgX (X = Cl-, Br-, I-) have been utilized in various chemistries for over 100 years. We report that replacing the halide in a Grignard reagent with a reactive borohydride anion adds a new synthetic dimension for these influential compounds. We synthesized the series RMgBH4 (R = Et, n-Bu, Ph, Bn) and characterized the reactivity toward both organic and inorganic molecules. Using butylmagnesium borohydride (BuMgBH4) as an exemplar, we demonstrate that these compounds possess unique reactivity due to the presence of reducing borohydride groups, resulting in tandem reactivity with organic amides/esters to generate secondary and primary alcohols. Molecular dynamics simulations indicate the stability of BuMgBH4 is comparable to that of Mg(BH4)2 + MgBu2, validating the Schlenk equilibrium in borohydride Grignard compounds. Metadynamics simulations confirm that the equilibrium is kinetically accessible through solvent-mediated processes. BuMgBH4 also reacts with CO2 and NH3, revealing potential uses for CO2 utilization and as a mixed-anion metal borohydride/amide precursor.

Original languageAmerican English
Pages (from-to)2823-2832
Number of pages10
Issue number20
StatePublished - 2022

Bibliographical note

Publisher Copyright:
© 2022 American Chemical Society.

NREL Publication Number

  • NREL/JA-5900-81695


  • coupling reactions
  • Grignard reagents
  • hydrogen storage
  • metal hydrides
  • organomagnesium chemistry


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