Abstract: Modern chemical synthetic methods, involving organometallic catalysts, are highly prized in the chemical industry and provide a multibillion-dollar driver for many economies. A key area of organometallic catalysis is its application in the fine chemical and pharmaceutical industries. Traditional catalysis in these areas is often: 1. expensive because of the reliance on rare-earth metals, 2. requires brute force (high temperatures and pressures), and 3. produces significant waste materials. The focus of this work is to use nickel, an earth-abundant transition metal (EAM), to develop catalysis that solves some of these problems so the overall cost to the chemical industry can be dramatically reduced. It is of central importance for modern chemical industry to establish new, greener processes that save energy and reduce waste.
The synthesis and catalytic properties of Ni(II) complexes, with the general formula Ni(NHC)[P(OR)3](Ar)Cl, will be described [1-3]. These complexes are air-stable and extremely effective precatalysts in the Suzuki-Miyaura and Buchwald-Hartwig cross-coupling reactions. The reaction protocols described allow for the cross-coupling of aryl chlorides at low catalytic loading to deliver a wide variety of functionalized biaryl and amine compounds. [4-6] Overall, these reaction protocols operate at room or mild temperatures and can be applied to a variety of electronically and sterically differentiated coupling partners. Insights into the mechanisms of these reactions, including the proposed formation of the catalytically active Ni(NHC)[P(Oi-Pr)3] and the resting-state species, are also reported.
Keywords: Nickel Catalysis, Phosphite, NHC, Homogeneous, Cross-Coupling.
Acknowledgements
The authors would like to acknowledge the discovery program of the Australian Research Council for funding (DP230100051).
References
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