Cluster Zintl compounds

Physical properties and detection of liquid Zintl compounds have been discussed and problems of gradual development of stoichiometries in non-clustering liquid ionic alloys, and their agreement with those persisting in the solid, have been considered. Neutron diffraction techniques and the results of their applications (Ga, Tl, alkali alloys) have been described. 

Abstract This review highlights how molecular Zintl compounds can be used to create new materials with a variety of novel opto-electronic and gas absorption properties. The generality of the synthetic approach described in this chapter on coupling various group-IV Zintl clusters provides an important tool for the design of new kinds of periodically ordered mesoporous semiconductors with tunable chemical and physical properties. We illustrate the potential of Zintl compounds to produce highly porous non-oxidic semiconductors, and we also cover the recent advances in the development of mesoporous elemental-based, metal-chalcogenide, and binary intermetallic alloy materials. The principles behind this approach and some perspectives for application of the derived materials are discussed. 

Let us focus on Ge and begin with three-connect clusters. A compound containing [Ge4]4- tetrahedra has been prepared from Na and Ge (Figure 2.23). [Ge]- is isoelectronic with As. In the sep count it is a three-electron cluster fragment like C-H. So the cluster is analogous to P4 with six two-center Ge-Ge bonds and four external lone pairs. One can see the power of the Zintl idea ME is equivalent to E where E is a p-block element one column to the right. 

Indium and thallium form a number of binary compounds with alkali metals in which the group 13 elements form well-defined anionic clusters (Zintl ions, see Section 1-9). Examples are K8Inu (Fig. 6-3) which has considerably fewer (2n-4) electrons than the minimum described by Wade s rules (2n + 2), KgIn10Zn and K10In10M (M = Ni, Pd, Pt).6 Closo-In16 and nido-Inu clusters have also been found. Thallium, too, forms Zintl clusters Na2H contains Tlf tetrahedra, while K8T1ii is similar to In, and KT1 contains Tl octahedra.7... 

Reactions of metal carbonyls with Zintl phases do not always yield the desired result. An example is the reaction of KSi with the metal carbonyls M(CO)6 (M = Cr, Mo, W) and the chromium complex Cr(CO)sNMe3. Instead of forming a structure with a Si4 anion, KSi reduces these transition metal compounds to form the anions, [M2(CO)io] . In addition, certain organometallic transition metal clusters have been synthesized that contain Zintl anions coordinated to the metal, but Zintl compounds are not used as the reagents. 

Further examples of formally subvalent main group compounds that contain element-element bonds but not necessarily clusters are the Zintl phases. The bonding in these has been described as the octet rule for all atoms . The archetypal Zintl compound is NaTl, in which charges are assigned as Na+ and Tl, representing a formal transfer of electrons from the more to the less electropositive element. The Tl ion can be considered to be a group 14 pseudoelement, and in fact exists in NaTl as a three-dimensional polyanionic diamond framework (TN) stuffed with Na+ cations. The Zintl concept is extended more broadly to other binary and ternary solid-state compounds, whose structures show the formation of element-element bonds in one, two, or three dimensions. ... 

All elements of the group form Zintl compounds with electropositive metals (see Topic D5 ). Continuous networks of covalently bonded atoms are generally found, rather than the clusters common with group 14. For example, NaAl and NaTl have tetrahedral diamond-like networks of A1 or Tl, which can be understood on the basis that AT and TF have the same valence electron count as carbon. 

The Zintl ions shown in Figure 13.12 are closo- or nido-clusters. The compounds Rb4Li2Sng and K4Li2Sng, which contain urac/j o-[Sn8] (Figure 13.13b), have been prepared by the direct fusion of tin metal with the respective alkali... 

Indium clusters have also recently been characterized, notably in intermetallic compounds. Thus, the Zintl phase, Rbzinj, (prepared by direct reaction between the two metals at I530°C) has layers of octahedral closo-lnf, clusters joined into sheets through exo bonds at four coplanar vertices. These four In atoms are therefore each bonded to five neighbouring In atoms at the comers of a square-based pyramid, whereas the remaining two (Irans) In atoms in the Ine cluster... 

Many liquid alloys, in particular, the alkali-group IV alloys, exhibit (Zintl) anion clustering and show strong effects of compound formation. A typical example of such Zintl systems are sodium-tin alloys. In the solid NaSn crystal the Zintl anions Sn appear [1]. An interesting question is the stability of these anions in the liquid. Furthermore, the electrical conductivity of these alloys shows a strong dependence on composition [2] For the limiting (sodium-rich or tin-rich) cases a metallic (small) conductivity appears, but for the nearly equimolar compositions a semi-metallic behavior - with a considerably smaller conductivity - is observed. 

This approach to the formation of metalloid molecular cluster compounds shows clearly the difference lfom Zintl-like phases which lately have been successfully... 

The development of the synthesis concept described here for metalloid clusters should ultimately be capable of extension to element combinations and therefore molecular nanostructured alloys, as several results on metalloid SiAl and SiGa clusters have shown [114, 88, respectively]. Such mixed clusters resemble the Zintl-type compounds that are under intense investigation by Corbett et al. [115, 124-126],... 

K4Ge4, can be described as a polyanionic compound (as a Zintl phase also) containing the ion Ge44. This tetrahedral ion can be considered a naked (that is without any ligands bounded to the vertices) tetrahedral cluster formed by a main group element (that is Ee = 5 3 = 5X4 = 20). The electron count, on the basis of the Ge valence electrons and of the ion charge results in Ee = 4 X 4 + 4 = 20. 

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