Issue 40, 2020

Coligand role in the NHC nickel catalyzed C–F bond activation: investigations on the insertion of bis(NHC) nickel into the C–F bond of hexafluorobenzene

Abstract

The reaction of [Ni(Mes2Im)2] (1) (Mes2Im = 1,3-dimesityl-imidazolin-2-ylidene) with polyfluorinated arenes as well as mechanistic investigations concerning the insertion of 1 and [Ni(iPr2Im)2] (1ipr) (iPr2Im = 1,3-diisopropyl-imidazolin-2-ylidene) into the C–F bond of C6F6 is reported. The reaction of 1 with different fluoroaromatics leads to formation of the nickel fluoroaryl fluoride complexes trans-[Ni(Mes2Im)2(F)(ArF)] (ArF = 4-CF3-C6F42, C6F53, 2,3,5,6-C6F4N 4, 2,3,5,6-C6F4H 5, 2,3,5-C6F3H26, 3,5-C6F2H37) in fair to good yields with the exception of the formation of the pentafluorophenyl complex 3 (less than 20%). Radical species and other diamagnetic side products were detected for the reaction of 1 with C6F6, in line with a radical pathway for the C–F bond activation step using 1. The difluoride complex trans-[Ni(Mes2Im)2(F)2] (9), the bis(aryl) complex trans-[Ni(Mes2Im)2(C6F5)2] (15), the structurally characterized nickel(I) complex trans-[NiI(Mes2Im)2(C6F5)] (11) and the metal radical trans-[NiI(Mes2Im)2(F)] (12) were identified. Complex 11, and related [NiI(Mes2Im)2(2,3,5,6-C6F4H)] (13) and [NiI(Mes2Im)2(2,3,5-C6F3H2)] (14), were synthesized independently by reaction of trans-[Ni(Mes2Im)2(F)(ArF)] with PhSiH3. Simple electron transfer from 1 to C6F6 was excluded, as the redox potentials of the reaction partners do not match and [Ni(Mes2Im)2]+, which was prepared independently, was not detected. DFT calculations were performed on the insertion of [Ni(iPr2Im)2] (1ipr) and [Ni(Mes2Im)2] (1) into the C–F bond of C6F6. For 1ipr, concerted and NHC-assisted pathways were identified as having the lowest kinetic barriers, whereas for 1, a radical mechanism with fluoride abstraction and an NHC-assisted pathway are both associated with almost the same kinetic barrier.

Graphical abstract: Coligand role in the NHC nickel catalyzed C–F bond activation: investigations on the insertion of bis(NHC) nickel into the C–F bond of hexafluorobenzene

Supplementary files

Article information

Article type
Edge Article
Submitted
03 Aug. 2020
Accepted
06 Okt. 2020
First published
06 Okt. 2020
This article is Open Access

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

Chem. Sci., 2020,11, 11009-11023

Coligand role in the NHC nickel catalyzed C–F bond activation: investigations on the insertion of bis(NHC) nickel into the C–F bond of hexafluorobenzene

M. W. Kuntze-Fechner, H. Verplancke, L. Tendera, M. Diefenbach, I. Krummenacher, H. Braunschweig, T. B. Marder, M. C. Holthausen and U. Radius, Chem. Sci., 2020, 11, 11009 DOI: 10.1039/D0SC04237D

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