Binuclear, High-Valent Nickel Complexes: Ni−Ni Bonds in Aryl–Halogen Bond Formation

Justin B. Diccianni, Chunhua Hu, Tianning Diao

Research output: Contribution to journalArticle

Abstract

Metal–metal bonds play a vital role in stabilizing key intermediates in bond-formation reactions. We report that binuclear benzo[h]quinoline-ligated NiII complexes, upon oxidation, undergo reductive elimination to form carbon–halogen bonds. A mixed-valent Ni(2.5+)–Ni(2.5+) intermediate is isolated. Further oxidation to NiIII, however, is required to trigger reductive elimination. The binuclear NiIII–NiIII intermediate lacks a Ni−Ni bond. Each NiIII undergoes separate, but fast reductive elimination, giving rise to NiI species. The reactivity of these binuclear Ni complexes highlights the fundamental difference between Ni and Pd in mediating bond-formation processes.

Original languageEnglish (US)
Pages (from-to)3635-3639
Number of pages5
JournalAngewandte Chemie - International Edition
Volume56
Issue number13
DOIs
StatePublished - Mar 20 2017

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Nickel
Oxidation
benzo(h)quinoline

Keywords

  • C−X bond formation
  • mixed-valent compounds
  • nickel–nickel bond
  • reaction mechanisms
  • reductive elimination

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Binuclear, High-Valent Nickel Complexes : Ni−Ni Bonds in Aryl–Halogen Bond Formation. / Diccianni, Justin B.; Hu, Chunhua; Diao, Tianning.

In: Angewandte Chemie - International Edition, Vol. 56, No. 13, 20.03.2017, p. 3635-3639.

Research output: Contribution to journalArticle

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