Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process

Olena V. Zenkina, Amir Karton, Dalia Freeman, Linda J W Shimon, Jan M L Martin, Milko van der Boom

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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
Number of pages8
JournalInorganic Chemistry
Volume47
Issue number12
DOIs
Publication statusPublished - Jun 16 2008

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ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Zenkina, O. V., Karton, A., Freeman, D., Shimon, L. J. W., Martin, J. M. L., & van der Boom, M. (2008). Directing aryl-I versus aryl-Br bond activation by nickel via a ring walking process. Inorganic Chemistry, 47(12), 5114-5121. https://doi.org/10.1021/ic702289n