Issue 25, 2023

Oxygen transfer reactivity mediated by nickel perfluoroalkyl complexes using molecular oxygen as a terminal oxidant

Abstract

Nickel perfluoroethyl and perfluoropropyl complexes supported by naphthyridine-type ligands show drastically different aerobic reactivity from their trifluoromethyl analogs resulting in facile oxygen transfer to perfluoroalkyl groups or oxygenation of external organic substrates (phosphines, sulfides, alkenes and alcohols) using O2 or air as a terminal oxidant. Such mild aerobic oxygenation occurs through the formation of spectroscopically detected transient high-valent NiIII and structurally characterized mixed-valent NiII–NiIV intermediates and radical intermediates, resembling O2 activation reported for some Pd dialkyl complexes. This reactivity is in contrast with the aerobic oxidation of naphthyridine-based Ni(CF3)2 complexes resulting in the formation of a stable NiIII product, which is attributed to the effect of greater steric congestion imposed by longer perfluoroalkyl chains.

Graphical abstract: Oxygen transfer reactivity mediated by nickel perfluoroalkyl complexes using molecular oxygen as a terminal oxidant

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Apr 2023
Accepted
03 Jun 2023
First published
06 Jun 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 7026-7035

Oxygen transfer reactivity mediated by nickel perfluoroalkyl complexes using molecular oxygen as a terminal oxidant

S. Deolka, R. Govindarajan, E. Khaskin, S. Vasylevskyi, J. Bahri, R. R. Fayzullin, M. C. Roy and J. R. Khusnutdinova, Chem. Sci., 2023, 14, 7026 DOI: 10.1039/D3SC01861J

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