Zintl phase

In chemistry, a Zintl phase is a product of a reaction between a group 1 (alkali metal) or group 2 (alkaline earth metal) and main group metal or metalloid (from groups 13, 14, 15, or 16). It is characterized by intermediate metallic–ionic bonding. Zintl phases are a subgroup of brittle, high-melting intermetallic compounds that are diamagnetic or exhibit temperature-independent paramagnetism and are poor conductors or semiconductors. This type of solid is named after German chemist Eduard Zintl who investigated them in the 1930s. The term "Zintl phases" was first used by Laves in 1941. In his early studies, Zintl noted that there was an atomic volume contraction upon the formation of these products and realized that this could indicate cation formation. He suggested that the structures of these phases were ionic, with complete electron transfer from the more electropositive metal to the more electronegative main group element. The structure of the anion within the phase is then considered on the basis of the resulting electronic state. These ideas are further developed in the Zintl–Klemm–Busmann concept, where the polyanion structure should be similar to that of the isovalent element. Further, the anionic sublattice can be isolated as polyanions (Zintl ions) in solution and are the basis of a rich subfield of main group inorganic chemistry.

History A "Zintl phase" was first observed in 1891 by M. Joannis, who noted an unexpected green colored solution after dissolving lead and sodium in liquid ammonia, indicating the formation of a new product. It was not until many years later, in 1930, that the stoichiometry of the new product was identified as Na4Pb9 by titrations performed by Zintl et al.; and it was not until 1970 that the structure was confirmed by crystallization with ethylenediamine (en) by Kummer. In the intervening years and in the years since, many other reaction mixtures of metals were explored to provide a great number of examples of this type of system. There are hundreds of such compounds composed of group 14 elements and group 15 elements, plus dozens of others beyond those groups, all spanning a variety of different geometries. Corbett has contributed improvements to the crystallization of Zintl ions by demonstrating the use of chelating ligands, such as cryptands, as cation sequestering agents. More recently, Zintl phase and ion reactivity in more complex systems, with organic ligands or transition metals, have been investigated, as well as their use in practical applications, such as for catalytic purposes or in materials science.

Zintl phases Zintl phases are intermetallic compounds that have a pronounced ionic bonding character. They are made up of a polyanionic substructure and group 1 or 2 counter ions, and their structure can be understood by a formal electron transfer from the electropositive element to the more electronegative element in their composition. Thus, the valence electron concentration (VEC) of the anionic element is increased, and it formally moves to the right in its row of the periodic table. Generally the anion does not reach an octet, so to reach that closed shell configuration, bonds are formed. The structure can be explained by the 8 − n rule (replacing the number of valence electrons, n, by VEC), making it comparable to an isovalent element. The formed polyanionic substructures can be chains (one-dimensional), rings, and other two-or three-dimensional networks or molecule-like entities. The Zintl line is a hypothetical boundary drawn between groups 13 and 14. It separates the columns based on the tendency for group 13 elements to form metals when reacted with electropositive group 1 or 2 elements and for group 14 and above to form ionic solids. The 'typical salts' formed in these reactions become more metallic as the main group element becomes heavier.

Synthesis Zintl phases can be prepared in regular solid state reactions, usually performed under an inert atmosphere or in a molten salt solution. Typical solid state methods include direct reduction of corresponding oxides in solution phase reactions in liquid ammonia or mercury. The product can be purified in some cases via zone refining, though often careful annealing will result in large single crystals of a desired phase.

Characterization Many of the usual methods are useful for determining physical and structural properties of Zintl phases. Some Zintl phases can be decomposed into a Zintl ion—the polyanion that composes the anionic substructure of the phase—and counter ion, which can be studied as described below. The heat of formation of these phases can be evaluated. Often their magnitude is comparable to those of salt formation, providing evidence for the ionic character of these phases. Density measurements indicate a contraction of the product compared to reactants, similarly indicating ionic bonding within the phase. X-ray spectroscopy gives additional information about the oxidation state of the elements, and correspondingly the nature of their bonding. Conductivity and magnetization measurements can also be taken. Finally, the structure of a Zintl phase or ion is most reliably confirmed via X-ray crystallography.

Examples An illustrative example: There are two types of Zintl ions in K12Si17; 2x Si4−4 (pseudo P4, or according to Wade's rules, 12 = 2n + 4 skeletal-electrons corresponding to a nido-form of a trigonal-bipyramid) and 1x Si4−9 (according to Wade's rules, 22 = 2n + 4 skeletal-electrons corresponding to a nido-form of a bicapped square antiprism) Examples from Müller's 1973 review paper with known structures are listed in the table below.

Exceptions There are examples of a new class of compounds that, on the basis of their chemical formulae, would appear to be Zintl phases, for example, K8In11, which is metallic and paramagnetic. Molecular orbital calculations have shown that the anion is (In11)7− and that the extra electron is distributed over the cations and, possibly, the anion antibonding orbitals. Another exception is the metallic InBi. InBi fulfills the Zintl phase requisite of element-element bonds but not the requisite of the polyanionic structure fitting a normal valence compound, i.e., the Bi–Bi polyanionic structure does not correspond to a normal valence structure such as the diamond Tl− in NaTl.

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