Issue 4, 2022

Aerobic oxidation-functionalization of the aryl moiety in van Koten's pincer complex (NCN)Ni(ii)Br: relevance to carbon–heteroatom coupling reactions promoted by high-valent nickel species

Abstract

The growing popularity of metal-promoted C–H functionalization methodologies has led to increased efforts aimed at improving our understanding of the mechanistic underpinnings of C–C and C-heteroatom bond forming steps. One approach to such mechanistic studies involves probing the reactivities of model complexes featuring chelate-stabilized M-hydrocarbyl moieties. The present study uses van Koten's (NCN)Ni(II)Br compound as a model for probing C-heteroatom coupling with protic substrates HX (X = NHR, OR). Our results establish the crucial importance of aerobic (oxidative) conditions for promoting reactivities that give the functionalized ligands NC(X)N. The importance of oxidation for the C-heteroatom bond formation is further deduced from the reaction of the structurally authenticated complex (NCN)Ni(OSiMe3) with CuBr2 to give the C–O functionalization product NC(OSiMe3)N.

Graphical abstract: Aerobic oxidation-functionalization of the aryl moiety in van Koten's pincer complex (NCN)Ni(ii)Br: relevance to carbon–heteroatom coupling reactions promoted by high-valent nickel species

Supplementary files

Article information

Article type
Paper
Submitted
29 окт 2021
Accepted
22 дек 2021
First published
30 дек 2021

New J. Chem., 2022,46, 1800-1807

Aerobic oxidation-functionalization of the aryl moiety in van Koten's pincer complex (NCN)Ni(II)Br: relevance to carbon–heteroatom coupling reactions promoted by high-valent nickel species

J. Cloutier, F. Zamani and D. Zargarian, New J. Chem., 2022, 46, 1800 DOI: 10.1039/D1NJ05162H

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