A Computational Study of Oxiranyllithium

[reaction: see text] Computational methods were used to determine the structure, bonding, and aggregation states of oxiranyllithium in the gas phase and in THF solution, at 200 and 298 K. THF solvation was modeled by microsolvation with explicit THF ligands, forming a supermolecule that includes the oxiranyllithium aggregate and its first solvation shell. Because oxiranyllithium has a chiral center, two diastereomeric dimers were formed, the RR and the RS, along with their enantiomers. Similarly, three diastereomers of the tetramer were formed, the RRRR, RRRS, and RRSS and their enantiomers. Oxiranyllithium was found to exist predominantly as the tetramer in the gas phase, while the dimer was the dominant species in THF solution. The relative concentrations of the different stereoisomers were calculated from equilibrium constants.