A 1,2‐Addition Pathway for C(sp2)−H Activation at a Dinickel Imide

A dinickel imido complex was synthesized using a redox‐active naphthyridine‐diimine supporting ligand. Upon coordination of an external ligand, the Ni2 core was disrupted, triggering an aromatic C−H activation reaction to generate a Ni2(μ‐NHAr)(Ar) species. This intermediate is capable of liberating...

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Bibliographic Details
Published in:Chemistry : a European journal 2017-06, Vol.23 (32), p.7694-7697
Main Authors: Powers, Ian G., Kiattisewee, Cholpisit, Mullane, Kimberly C., Schelter, Eric J., Uyeda, Christopher
Format: Article
Language:English
Subjects:
Activation
amination
Carbazole
Chemistry
C−H activation
Heating
Ligands
metal–metal interactions
nickel
nitrene
Phenanthridine
Synthesis
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Summary:A dinickel imido complex was synthesized using a redox‐active naphthyridine‐diimine supporting ligand. Upon coordination of an external ligand, the Ni2 core was disrupted, triggering an aromatic C−H activation reaction to generate a Ni2(μ‐NHAr)(Ar) species. This intermediate is capable of liberating free carbazole and phenanthridine products upon heating or treatment with excess tBuNC. Collectively, these studies establish a kinetically facile 1,2‐addition mechanism for C(sp2)−H activation, taking advantage of cooperative reactivity between two Ni centers. Cooperative reactivity: An isolable dinickel nitrene complex is shown to activate aromatic C−H bonds by a 1,2‐addition mechanism. Heterocyclic products can be liberated from the C−H activated intermediate through thermal or ligand‐induced reductive elimination.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201701855