Magnetic ordering in inorganic materials is generally considered to be a mechanism for structures to stabilize open shells of electrons. The intermetallic phase Mn2Hg5 represents a remarkable exception: its crystal structure is in accordance with the 18-n bonding scheme and non-spin-polarized density functional theory (DFT) calculations show a corresponding pseudogap near its Fermi energy. Nevertheless, it exhibits strong antiferromagnetic ordering virtually all the way up to its decomposition temperature. In this Article, we examine how these two features of Mn2Hg5 coexist through the development of a DFT implementation of the reversed approximation Molecular Orbital (raMO) analysis. In the non-spin-polarized electronic structure, the DFT-raMO approach confirms that Mn2Hg5 adheres to the 18-n rule: its chains of Mn atoms are linked through isolobal triple bonds, with three electron pairs being shared at each Mn-Mn contact in one sigma-type and two pi-type functions. Because each Mn atom has 6 isolobal Mn-Mn bonds, it achieves a filled 18-electron count at the compounds electron concentration of 18 - 6 = 12 electrons/Mn. A pseudogap thus occurs at the Fermi energy. Upon the introduction of antiferromagnetic order, the original pseudogap widens and deepens, suggesting enhancement of a stabilizing effect already present in the nonmagnetic state. A raMO analysis reveals that antiferromagnetism enlarges the gap by allowing diradical character to enter into the Mn-Mn isolobal pi bonds, reminiscent of the dissociation of a classic covalent bond. Antiferromagnetism is accompanied by residual bonding in the pi system, making Mn2Hg5 a vivid realization of the concept of covalent magnetism.