Tridentate Ligand for a T-Shaped Nickel(I) Radical

Tridentate Ligand for a T-Shaped Nickel(I) Radical

Author: Chemistry – A European Journal

Sakya S. Sen, CSIR-National Chemical Laboratory, Pune, India, and Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India, and colleagues have synthesized a nickel(I) radical with a T-shaped structure. The team used KSi(SiMe3)3 as a reducing agent to convert a Ni(II) chloride complex with a picolyl-group-containing β-diketiminato ligand, i.e., [2,6-iPr2-C6H3NC(Me)CHC(Me)NH(CH2py)] Ni(II)Cl, into the desired Ni(I) radical (pictured below).



The formation of the Ni(I) radical was confirmed using electron paramagnetic resonance (EPR) measurements and a reaction with the radical scavenger TEMPO, resulting in the formation of an unusual three-membered nickeloxaziridine complex.

The researchers tested the radical’s activity for dihydrogen activation, resulting in the formation of a monomeric Ni hydride under ambient reaction conditions. The Ni(I) radical also homolytically cleaved the S‒S and Se‒Se bonds of a disulfide and a diselenide. This led to interesting C–C coupled products in which two units of the Ni complex are connected via their ligands.

Overall, the work provides a unique approach to synthesizing and stabilizing Ni(I) radicals. This approach could be useful in organic synthesis and catalysis.


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