Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles

Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3‐cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO–LUMO gap and enhanced the near IR absorption property. At the core: Cyanide, phenylthiolate, and phenoxide anions react with an antiaromatic nickel(II) norcorrole complex in the absence of a catalyst to yield substitution products. The reaction takes place regioselectively at the β‐positions proximal to the meso substituents. The distinct antiaromatic property of the norcorrole core is retained in the functionalized products.