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

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

Research output: Contribution to journalArticle

Abstract

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
JournalInorganic Chemistry
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

regeneration
routes
catalysts
cycles
Catalysts
deactivation
Ligands
Catalyst deactivation
Alkanes
Diamines
simulation
Equilibrium constants
Seawater
Autocorrelation
ligands
Density functional theory
Molecular dynamics
butenes
diamines
alkanes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Molecular Simulation of the Catalytic Regeneration of n BuLi through a Hydrometalation Route . / Lee, Mal Soon; Glezakou, Vassiliki Alexandra; Rousseau, Roger; McGrail, B. Peter.

In: Inorganic Chemistry, 01.01.2019.

Research output: Contribution to journalArticle

@article{306629527c6c4f80b5b7c1194056a25b,
title = "Molecular Simulation of the Catalytic Regeneration of n BuLi through a Hydrometalation Route",
abstract = "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.",
author = "Lee, {Mal Soon} and Glezakou, {Vassiliki Alexandra} and Roger Rousseau and McGrail, {B. Peter}",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/acs.inorgchem.8b02910",
language = "English",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",

}

TY - JOUR

T1 - Molecular Simulation of the Catalytic Regeneration of n BuLi through a Hydrometalation Route

AU - Lee, Mal Soon

AU - Glezakou, Vassiliki Alexandra

AU - Rousseau, Roger

AU - McGrail, B. Peter

PY - 2019/1/1

Y1 - 2019/1/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85061525742&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85061525742&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.8b02910

DO - 10.1021/acs.inorgchem.8b02910

M3 - Article

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -