Benzothiazole Nickelation: An Obstacle to the Catalytic Arylation of Azoles by Cyclopentadienyl Nickel N-Heterocyclic Carbene Complexes

NiCp†L(NHC)](+) complexes (Cp† = Cp (η5-C5H5), Cp* (η5-C5Me5); NHC = N-heterocyclic carbene; L = Cl− or NCMe) have been tested as pre-catalysts for the direct arylation of benzothiazole in the presence of an alkoxide. Only the pentamethylcyclopentadienyl derivative, [NiCp*Cl(IMes)] (IMes = 1,3-bis(2,4,6-trimethylphenylimidazol-2-ylidene), enabled low conversion to the desired coupling product with phenyl iodide as the electrophilic coupling partner. In contrast, all cyclopentadienyl complexes proved to be inactive. 1H NMR studies of the “catalytic” reaction mixtures demonstrate that they cleanly convert to an unreactive C(2)-benzothiazolyl derivative, whose identity has been confirmed by an independent synthesis and characterization. The latter constitutes a potential energy well that quenches all further reactivity, and provides a rare example of C(2)-metallated azolyl complex.