Computational exploration of the copper(I)-catalyzed conversion of hydrazones to dihalogenated vinyldiazene derivatives

Abstract

This computational study explores the copper (I) chloride catalyzed synthesis of (E)-1-(2,2-dichloro-1-phenylvinyl)-2-phenyldiazene (2Cl-VD) from readily available hydrazone derivative and carbon tetrachloride (CCl₄). 2Cl-VD has been extensively utilized to synthesize variety of heterocyclic organic compounds in mild conditions. The present computational investigations primarily focus on understanding the role of copper (I) and N¹,N¹,N²,N²-tetramethylethane-1,2-diamine (TMEDA) in this reaction, TMEDA often being considered a proton scavenger by experimentalists. Considering TMEDA as a ligand significantly alters the energy barrier. In fact, it is only 8.3 kcal/mol higher compared to the ligand-free (LF) route for the removal of a chlorine atom to form the radical ·CCl₃ but the following steps are almost barrierless. This intermediate then participates in attacking the electrophilic carbon in the hydrazone. Crucially, the study reveals that the overall potential energy surface is thermodynamically favorable, and the theoretical turnover frequency (TOF) value is higher in the case of Cu(I)-TMEDA complex catalyzed pathway.