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We report a new family of ternary 111 hexagonal LnAuSb (Ln = La-Nd, Sm)compounds that, with a 19 valence electron count, has one extra electroncompared to all other known LnAuZ compound. The "19th" electron is accommodatedby Au-Au bonding between the layers; this Au-Au interaction drives the phasesto crystallize in the YPtAs-type structure rather than the more commonLiGaGe-type. This is critical, as the YPtAs structure type has thesymmetry-allowed band crossing necessary for the formation of Dirac semimetals.Band structure, density of stats, and crystal orbital calculations confirm thispicture, which results in a nearly complete band gap between full and emptyelectronic states and stable compounds; we can thus present a structuralstability phase diagram for the LnAuZ (Ln = Ge, As, Sn, Sb, Pb, Bi) family ofphases. Those calculations also show that LaAuSb has a bulk Dirac cone belowthe Fermi level. The YPtAs-type LnAuSb family reported here is an example ofthe uniqueness of gold chemistry applied to a rigidly closed shell system in anunconventional way.

Gold-Gold Bonding: The Key to Stabilizing the 19-Electron Ternary Phases LnAuSb (Ln = La-Nd and Sm) as New Dirac Semimetals