Molecular Simulation of the Catalytic Regeneration of n BuLi through a Hydrometalation Route

Mal Soon Lee, Vassiliki Alexandra Glezakou, Roger Rousseau, B. Peter McGrail

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1 Citation (Scopus)


Efficient regeneration of organolithium compounds is a challenging aspect in the process of novel organometathetical catalytic cycles. One of these catalytic cycles is a newly suggested method for Mg production from seawater that capitalizes on the rich chemistry of Grignard reagents. The proposed three-step catalytic cycle with Cp 2 MClL catalyst (M = Ti, Zr; L = select organic ligands) requires the regeneration of n BuLi from Li(s), butene, and H 2 . The potential of this approach is evaluated with density functional theory-based molecular simulations. The results reveal that the high affinity of Li toward Cl and N results in the formation of alkanes, and the strong coupling between the catalyst and BuLi leads to catalyst deactivation. To improve its catalytic performance, we proposed the use of a diamine cocatalyst and a modified catalyst with a ligand that does not contain N, which would help release BuLi from the vicinity of the catalytic center. Ab initio molecular dynamics simulations at 298 K in explicit solvent (THF) were used to estimate the Gibbs free energetics and equilibrium constants obtained from the vibrational density of states using velocity autocorrelation functions. The results show a marked improvement in the free energetics with lower barriers toward the completion of the catalytic cycle and suppression of deactivation channels.

Original languageEnglish
Pages (from-to)3033-3040
Number of pages8
JournalInorganic Chemistry
Issue number5
Publication statusPublished - Mar 4 2019

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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