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

Justin B. Diccianni; Chunhua Hu; Tianning Diao

doi:10.1002/anie.201611572

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

Justin B. Diccianni, Chunhua Hu, Tianning Diao

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Metal–metal bonds play a vital role in stabilizing key intermediates in bond-formation reactions. We report that binuclear benzo[h]quinoline-ligated Ni^II 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 Ni^III, however, is required to trigger reductive elimination. The binuclear Ni^III–Ni^III intermediate lacks a Ni−Ni bond. Each Ni^III undergoes separate, but fast reductive elimination, giving rise to Ni^I species. The reactivity of these binuclear Ni complexes highlights the fundamental difference between Ni and Pd in mediating bond-formation processes.

Original language	English (US)
Pages (from-to)	3635-3639
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	13
DOIs	https://doi.org/10.1002/anie.201611572
State	Published - Mar 20 2017

Keywords

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

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201611572

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

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.",

keywords = "C−X bond formation, mixed-valent compounds, nickel–nickel bond, reaction mechanisms, reductive elimination",

author = "Diccianni, {Justin B.} and Chunhua Hu and Tianning Diao",

note = "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: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = mar,

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doi = "10.1002/anie.201611572",

language = "English (US)",

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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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DO - 10.1002/anie.201611572

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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ER -

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

Abstract

Keywords

ASJC Scopus subject areas

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