A New Interpretation of the Reaction Pathway of Deprotonative Metalation with TMP−Zn-ate/TMEDA Complex [TMEDA·Na(μ-<i>^t</i>Bu)(μ-TMP)Zn(<i>^t</i>Bu)]

Abstract

Density functional theory (DFT) calculations of possible reaction pathways and mechanisms for the deprotonation of benzene with Mulvey's reagent, TMEDA.Na(micro-R)(micro-TMP)Zn(R) (TMEDA=N,N,N',N'-tetramethylethylenediamine, R = alkyl, TMP = 2,2,6,6-tetramethylpiperidide) indicate that the deprotonation of benzene with Mulvey's reagent proceeds through a stepwise mechanism, not a one-step mechanism. In the first step, deprotonation involving the TMP ligand on the reagent is kinetically more favorable than that involving the alkyl ligand.