Organozinc reagents in solution: insights from ab initio molecular dynamics and X-ray absorption spectroscopy

Organozinc reagents play a critical role in synthesis, yet our comprehension of their structure-reactivity relationships is limited by a lack of information about their structures in solution. This study introduces a computational workflow, validated by X-ray absorption spectroscopy, to investigate organozinc reagents in solution. The solvation states of ZnCl2, ZnMeCl and ZnMe2 were explored using ab initio molecular dynamics (metadynamics and Blue Moon sampling) within an explicit solvent cage. The study revealed the existence of various solvation states at room temperature, providing clarity on the previously debated structure of ZnMe2 in THF solution. These findings were confirmed by near- edge X-ray absorption spectroscopy (XANES) interpreted using time-dependent density functional theory (TD-DFT) calculations.