Solid state interactions in the La-Au-Mg system: phase equilibria, novel compounds and chemical bonding

Gold intermetallic chemistry is very rich, covering different classes of compounds ranging from the Hume-Rothery to Zintl phases to polar intermetallics to quasicrystals. Au's relativistic effects are frequently mentioned as responsible for the peculiar structural and physical properties of its compounds, nonetheless the aspects of chemical bonding are far to be clearly understood. In this work, the La-Au-Mg system was targeted for the discovery of new gold intermetallics and their structural and chemical bonding characterization. Studies on solid state interactions resulted in the construction of a partial La-Au-Mg isothermal section at 400 °C. The high reactivity between the constituents is reflected by the formation of five intermetallic compounds in the concentration range of less than 50 at% of Au. A complete crystallographic study was conducted for four of them, namely La1.82Au3+xMg14.36-x (0 ≤ x ≤ 0.90, hP42-3.64-CeMg10.3), La3Au4-xMg12+x (0 ≤ x ≤ 0.75, hP38-Gd3Ru4Al12), LaAuMg2 (oS16-MgCuAl2) and LaAu1+xMg1-x (0 ≤ x ≤ 0.15, hP9-ZrNiAl). A unifying description based on the different stacking sequences of equal slabs along the c-axis is proposed for these intermetallics. Chemical bonding in LaAuMg2 was studied by following the position space approach and including relativistic effects. Among the peculiarities of this LaMg2Au auride, there are two-atomic La-Au bonds showing a classical polar covalent character and that form distorted hexagonal planar layers and multi-atomic bonds involving Mg species. One of these is interpreted as a Mg-Mg bond supported by the neighbouring La and Au atoms, explaining the Mg reduced oxidation state (close to +1) in this compound.