title: A new interpretation of the reaction pathway of deprotonative metalation with TMP-Zn-ate/TMEDA Complex [TMEDA.Na(micro-tBu)(micro-TMP)Zn(tBu)].
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.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku Tokyo 113-0033, Japan.
authors.forename: Daisuke
authors.initials: D
authors.lastname: Nobuto
authors.forename: Masanobu
authors.initials: M
authors.lastname: Uchiyama
mesh_terms: D000478:Alkylation; D001554:Benzene / Q000737:chemistry; D005029:Ethylenediamines / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D011522:Protons; D017967:Zinc Compounds / Q000737:chemistry*
chemical_list: D005029:Ethylenediamines; D008024:Ligands; D011522:Protons; D017967:Zinc Compounds; C005798:N,N,N',N'-tetramethylethylenediamine; D001554:Benzene