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The Zintl phase Ba 3 Si 4 has been synthesized from the elements at 1273 K as a single phase. No homogeneity range has been found. The compound decomposes peritectically at 1307(5) K to BaSi 2 and melt. The butterfly-shaped Si 4 6Ϫ Zintl anion in the crystal structure of Ba 3 Si 4 (Pearson symbol tP28, space group P4 2 /mnm, a ϭ 8.5233(3) Å , c ϭ 11.8322(6) Å ) shows only slightly different Si-Si bond lengths of d(SiϪSi) ϭ 2.4183(6) Å (1ϫ) and 2.4254(3) Å (4ϫ). The compound is diamagnetic with χ ഠ Ϫ50 ϫ 10 Ϫ6 cm 3 mol Ϫ1 . DC resistivity measurements show a high electrical resistivity (ρ(300 K) ഠ 1.2 ϫ 10 Ϫ3 Ω m) with positive temperature gradient dρ/dT. The temperature dependence of the isotropic signal shift and the spin-lattice relaxation times in 29 Si 1651 NMR spectroscopy confirms the metallic behavior. The experimental results are in accordance with the calculated electronic band structure, which indicates a metal with a low density of states at the Fermi level. The electron localization function (ELF) is used for analysis of chemical bonding. The reaction of solid Ba 3 Si 4 with gaseous HCl leads to the oxidation of the Si 4 6Ϫ Zintl anion and yields nanoporous silicon.

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