A prospective connection between Hume-Rothery inspired TM/E (TM = transition metal; E = Al, Ga, Zn) complexes and clusters with the related solid-state intermetallic TM/E compounds is presented with respect to the industrially relevant catalytic semihydrogenation of acetylene. The theoretical study dealing with [Ni(ER)n(C2Hx)4-n] (x = 2, 4; R = CH3, C5Me5,) calculated on the DFT level of theory shows intriguing structural and electronic properties of the examined complexes. Different Ni-E complexes show preferred binding of C2H2 over C2H4 in bridging positions between Ni and E depending on the [Ni(ER)n] fragment. These findings render molecular TM/E systems, such as Ni/Zn, promising candidates to mimic key intermediates of intermetallic catalysts applied in heterogeneous hydrogenation reactions. We put these findings into the context of existing synthetic results and illustrate different experimental approaches to obtain compounds of the general formula [TMaEb](Cp*)c(UHC)d (UHC = unsaturated hydrocarbon ligands) as potential surface models.