Alkali Metal Group 14 Zintl Clusters

The polyhedral boranes and carboranes discussed above may be regarded as boron clusters in which the single external orbital of each vertex atom helps to bind an external hydrogen or other monovalent atom or group. Post-transition main group elements are known to form clusters without external ligands bound to the vertex atoms. Such species are called bare metal clusters for convenience. Anionic bare metal clusters were first observed by Zintl and co-workers in the 1930s [2-5], The first evidence for anionic clusters of post-transition metals such as tin, lead, antimony, and bismuth was obtained by potentiometric titrations with alkali metals in liquid ammonia. Consequently, such anionic post-transition metal clusters are often called Zintl phases. 

Group 14 alkali metal bonded complexes Group 1-Group 14, 2, 55 Zintl clusters, 2, 24... 

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... 

The increasing charge on the group-13 and group-15 cluster ions must be counterbalanced by a larger number of counter ions. A large value of n requires more and thus smaller counter ions. For this reason, polyhedral Zintl ions of group-13 elements occur preferentially in Zintl phases with alkali- or alkaline-earth metal... 

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. 

The term Zintl phase is applied to solids formed between either an alkali- or alkaline-earth metal and a main group p-block element from group 14, 15, or 16 in the periodic table. These phases are characterized by a network of homonuclear or heteronuclear polyatomic clusters (the Zintl ions), which carry a net negative charge, and that are neutralized by cations. Broader definitions of the Zintl phase are sometimes used. Group 13 elements have been included with the Zintl anions and an electropositive rare-earth element or transition element with a filled d shell (e.g. Cu) or empty d shell (e.g. Ti) has replaced the alkali- or alkaline-earth element in some reports. Although the bonding between the Zintl ions and the cations in the Zintl phases is markedly polar, by our earlier definition those compounds formed between the alkali- or alkaline-earth metals with the heavier anions (i.e. Sn, Pb, Bi) can be considered intermetallic phases. 

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