A DFT-derived model predicts solvation-dependent configurational stability of organolithium compounds: a case study of a chiral alpha-thioallyllithium compound.
Density functional theory calculations (B3LYP/6-31+G*) were performed to evaluate a model previously published by us which suggests that aggregation and solvation of organolithium compounds can be of large importance for their configurational stability. In this study, we demonstrate how THF solvation of the monomer of a chiral alpha-thioallyllithium compound impedes the racemization, while upon dimerization the inversion process accelerates. These findings agree with experiments performed by Hoppe and co-workers. These findings may be used to further develop organolithium compounds which should be designed to resist aggregation and efficient transition-state solvation.
Brandt
Peter
P
Department of Structural Chemistry, Biovitrum AB, 112 76 Stockholm, Sweden.
Haeffner
Fredrik
F
D008094:Lithium / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D012996:Solutions; D013438:Sulfhydryl Compounds / Q000737:chemistry
D009942:Organometallic Compounds; D012996:Solutions; D013438:Sulfhydryl Compounds; D008094:Lithium