Late first-row transition metal imido complexes have been actively studied for their reactivities in C-H activation and nitrene group transfer reactions. Our group has been working on incorporating Lewis acid functional groups in the metal’s secondary sphere in order to impart a divergent reactivity and selectivity. This presentation will describe the synthesis of a series of nickel diphosphine complexs with an appended borane, and the formation of imide species from organoazides. We will show a nickel imide species formed from 1-azidoadamantane exhibits reactivity toward sp<sup>2</sup> C-H activation of arenes to form LNi(Ar)(NHAd) as a result of an appended Lewis acid. This presentation will outline experimental and computational efforts in elucidating the nature of the reactive species and illustrate principles of ligand design that can be used to tune reaction selectivity. We will also present our ongoing endeavours in utilizing low valent nickel complexes for bond activation and small molecule activation.

Lewis acid-imparted divergent reactivity of nickel imido and related species

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ACS Fall 2022

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