Intermetallic compounds composed of transition metals and semimetals or post-transition metals have been shown to exhibit elevated selectivity in olefins and aromatics production and other reactions that require control of C=C activation and functionalization. The vast number of element combinations available for intermetallic compound production necessitates down-selecting to isolate catalytically useful compositional spaces. In this study, we have investigated the semi-hydrogenation of acetylene over isoelectronic intermetallic compounds composed of nickel and the boron group elements at a bulk stoichiometry of 1:1. We have isolated that orbital overlap between IMC constituent elements tracks well with the nature of their bulk bonding, surface reactivity, and catalytic preference for the semihydrogenation of acetylene to ethylene. The trend isolated appears to be universal and marks a subspace within intermetallic compounds that is promising to focus further studies upon. Results also suggest the possibility of accessing New Bronsted-Evans-Polanyi relationships over a subspace of intermetallic compounds. (C) 2019 Elsevier Inc. All rights reserved.