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.

Chemical Science
Maximilian W Kuntze-FechnerUdo Radius

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-C6F4 2, C6F5 3, 2,3,5,6-C6F4N 4, 2,3,5,6-C6F4H 5, 2,3,5-C6F3H2 6, 3,5-C6F2H3 7) 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. Si...Continue Reading

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Citations

Feb 18, 2021·Chemical Reviews·Ya-Ming TianTodd B Marder
May 26, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Mirjam J Krahfuss, Udo Radius
Jul 1, 2021·Chemistry : a European Journal·Sara SabaterMichael K Whittlesey
Oct 8, 2021·Chemical Reviews·Shubhankar Kumar BoseTodd B Marder

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