Abstract
AbstractAroyl complexes of the type trans‐[Ni(iPr2Im)2(X)(C(O)Ar)] (X = Cl and Ar = Ph (2), 4‐tBu‐C6H4 (3) and C6F5 (4) and X = Br and Ar = Ph (5)) were prepared by oxidative addition reactions of carboxylic acid halides with the dinuclear nickel(0) complex [Ni2(iPr2Im)4(COD)] (1) (iPr2Im = 1, 3‐diisopropylimidazolin‐2‐ylidene; COD = 1, 5‐cyclooctadien). The reported compounds were characterized by multinuclear NMR spectroscopy, EI‐mass spectroscopy, IR spectroscopy, and elemental analysis. The benzoyl chloride complex trans‐[Ni(iPr2Im)2(Cl)(C(O)Ph)] (2) as well as its bromide analogue trans‐[Ni(iPr2Im)2(Br)(C(O)Ph)] (5) were additionally structurally characterized by single‐crystal X‐ray crystallography. NMR spectra of the crude products revealed the formation of minor amounts of the corresponding bis(halide) complexes trans‐[Ni(iPr2Im)2(Cl)2] (6) and trans‐[Ni(iPr2Im)2(Br)2] (7), depending on the aroyl halide used. Decarbonylation of the benzoyl complexes was observed upon irradiation of the complexes 2 and 5 with UV light. NMR analysis of the resulting mixtures of products revealed the formation of the phenyl halide complexes trans‐[Ni(iPr2Im)2(Cl)(Ph)] (8) and [Ni(iPr2Im)2(Br)(Ph)] (9), as well as the formation of the bis(halide) complexes 6 and 7.
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