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

Journal Article · · Organometallics
 [1];  [1];  [2];  [2];  [3];  [3];  [1];  [4];  [5];  [1];  [6];  [6];  [7];  [8];  [6];  [6]
  1. Sandia National Laboratory (SNL-CA), Livermore, CA (United States)
  2. Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  4. Sandia National Laboratory (SNL-CA), Livermore, CA (United States); Technische University Dresden (Germany)
  5. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  6. Sandia National Laboratories, 7011 East Avenue, Livermore, California 94550, United States
  7. National Renewable Energy Laboratory, 15013 Denver W Parkway, Golden, Colorado 80401, United States
  8. Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United States
+ Show Author Affiliations

Grignard reagents of general formula RMgX (X = Cl-, Br-, I-) have been utilized in various chemistries for over 100 years. Here, we report that replacing the halide in a Grignard reagent with a reactive borohydride anion adds a new synthetic dimension for these influential compounds. Here, 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.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office
Grant/Contract Number:
AC05-76RL01830; NA0003525; AC36-08GO28308; AC52-07NA27344
OSTI ID:
1894617
Alternate ID(s):
OSTI ID: 1897519
OSTI ID: 1899981
OSTI ID: 2204925
Report Number(s):
SAND2022-14257J; 710932
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 20 Vol. 41; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Grignard reagents
alcohols
anions
coupling reactions
hydrogen storage
metal hydrides
molecular structure
organomagnesium chemistry
reactivity
reagents