TY - JOUR
T1 - Binuclear, High-Valent Nickel Complexes
T2 - Ni−Ni Bonds in Aryl–Halogen Bond Formation
AU - Diccianni, Justin B.
AU - Hu, Chunhua
AU - Diao, Tianning
N1 - Funding Information:
We thank Prof. Carsten Milsmann (University of West Virginia) for helpful discussions and Nadia Leonard (Chirik lab, Princeton University) for assistance in recording EPR spectra. This work was supported by the National Science Foundation under award number CHE-1654483 and New York University.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/3/20
Y1 - 2017/3/20
N2 - 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.
AB - 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.
KW - C−X bond formation
KW - mixed-valent compounds
KW - nickel–nickel bond
KW - reaction mechanisms
KW - reductive elimination
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U2 - 10.1002/anie.201611572
DO - 10.1002/anie.201611572
M3 - Article
C2 - 28194838
AN - SCOPUS:85013074537
SN - 1433-7851
VL - 56
SP - 3635
EP - 3639
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 13
ER -