Carbon Halide Bond Activation of Benzyl Chloride and Benzyl Bromide Using An NHC‐Stabilized Nickel(0) Complex

A first example of the application of an NHC‐stabilized nickel complex as a catalyst in Suzuki–Miyaura cross‐coupling reactions of alkyl halides is reported. The complexes trans‐[Ni(iPr2Im)2(X)(CH2Ph)] (X = Cl 2 and Br 3) were prepared from the reactions of benzyl chloride and benzyl bromide and the dinuclear complex [Ni2(iPr2Im)4(COD)] (1). These compounds were fully characterized by elemental analysis, IR spectroscopy, multinuclear NMR spectroscopy, and X‐ray crystallography. Based on these stoichiometric oxidative addition reactions catalytic Suzuki–Miyaura cross‐coupling reactions have been performed. Complex 1 is an effective catalyst for the Suzuki–Miyaura cross‐coupling reaction of benzyl chloride and phenylboronic acid. Quantitative conversion of benzyl chloride with a high selectivity to the cross‐coupling product diphenylmethane was achieved after two hours reaction time using three equivalents phenylboronic acid, three equivalents cesium fluoride and 1.22 mol‐% [Ni2(iPr2Im)4(COD)] (1) as a catalyst.