Solvothermal reactions in methanol of nickel acetate tetrahydrate, Ni(OAc) 2 ·4H 2 O, with benzonitrile derivatives NC(C 6 H 4 )X, where X is one of the electron withdrawing substituents –CN, –NO 2 , or –CF 3 , located at the m- or p-positions relative to –CN, yield complexes of the general formula Ni{HNC(R)–NC(R)–NH} 2 . More specifically, 3-nitrobenzonitrile, 4-nitrobenzonitrile, 1,3-dicyanobenzene, 1,4-dicyanobenzene, and ααα-trifluoro-p-toluonitrile are found to react with Ni(OAc) 2 ·4H 2 O to yield Ni{HNC(R)–NC(R)–NH} 2 , where R=3-(NO 2 )C 6 H 4 , 4-(NO 2 )C 6 H 4 , 3-(CN)C 6 H 4 , 4-(CN)C 6 H 4 , or 4-(CF 3 )C 6 H 4 , respectively. Analogous reactions of nitriles lacking electron withdrawing groups do not occur under similar conditions. Solid-state structures have been determined for the complexes with p-NO 2 , p-CN, and p-CF 3 substituents on the phenyl rings. In addition, we describe density functional theory (DFT) and natural bonding orbital theory (NBO) studies on a simplified analog of these compounds, aimed at understanding their molecular bonding. It is shown that the new compounds for which solid-state structures have been determined are model examples of coordination compounds containing robust ω-bonds.