Quantum Chemical Investigation of Dimerization in the Schlenk Equilibrium of Thiophene Grignard Reagents.

ABSTRACT: The Schlenk equilibrium of Grignard reagents describes the intricate relationships between monomers, aggregates, and exchange products. The core step of the Schlenk equilibrium, formally 2RMgX ⇌ R₂Mg + MgX₂, has been subject to computational studies of simple methyl Grignards and NMR determination of thermodynamics. These studies neglect the effect the R group may have on the accessibility of intermediates in the Schlenk equilibrium. In this study, computational reaction discovery tools were employed to thoroughly search the chemical space for feasible dimerizations and pathways to ligand exchange for thiophene Grignards. Three bridged dimers, μ-(Cl, C), μ-(Cl, Cl), and μ-Cl, were found to be vital intermediates, which are stabilized by π-interactions involving the th

SUBMITTER: Curtis ER 

PROVIDER: S-EPMC7170039 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature