We report the reaction of a sterically congested NHC-Zn(CH 2CH3)2 Lewis adduct (1) prepared through reaction of an equimolar ratio of 1,3-di-tert-butylimidazol-2-ylidene and diethyl zinc, with various substituted phenols (4-tert-butyl-phenol, 2,6-di-tert-butyl-4-methyl phenol, and 1-bromo-4,6-di-tert-butyl phenol). The NHC-Zn dative bond was cleaved in each of the reactions with the substituted phenols to afford the corresponding ionic complexes of imidazolium cation and aryloxo-zincate, [{(4-CMe3C6H4O) 2Zn(-OC6H4-4-CMe3)} 2{(1,3-(CMe3)2-ImCH}2] (2), [{(2,6-(CMe3)2-4-Me-C6H3O) 2}Zn{(1,3-(Cme3)2-ImCH}] (3), and [{(1-Br-3,5-(Cme3)2C6H2O) 2}2-Zn{(1,3-(CMe3)2-ImCH}] (4), where 1,3-(CMe3)2-ImCH) is imidazolium carbocation. The molecular structures of 1-4 were established by X-ray diffraction analyses and from the solid-state structures of 2-4, it was confirmed that, in all the compounds, zinc ions are coordinated through substituted phenolate groups. © 2014 © 2014 Taylor & Francis.