Directing Aryl-I versus Aryl-Br Bond Activation by Nickel via a Ring Walking Process

O.V. Zenkina, Amir Karton, D. Freeman, L.J.W. Shimon, J.M.L. Martin, M.E. Van Der Boom

Research output: Contribution to journalArticle

52 Citations (Scopus)

Abstract

Activation of a strong aryl−Br bond of a halogenated vinylarene by nickel(0) is demonstrated in the presence of aryl−I containing substrates. η2-Coordination of Ni(PEt3)2 to the C═C moiety of halogenated vinylarenes is kinetically preferable and is followed by an intramolecular aryl−halide bond activation process. This “ring-walking” process is quantitative and proceeds under mild reaction conditions in solution. Mechanistic studies indicate that the metal insertion into the aryl−halide bond is not the rate-determining step. The reaction obeys first-order kinetics in the η2-coordination complexes with almost identical activation parameters for Br and I derivatives. The ring-walking process is kinetically accessible as shown by density functional theory (DFT) calculations at the PBE0/SDB-cc-pVDZ//PBE0/SDD level of theory.
Original languageEnglish
Pages (from-to)5114-5121
JournalInorganic Chemistry
Volume47
Issue number12
Early online date17 May 2008
DOIs
Publication statusPublished - 16 Jun 2008

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