Metalloid cluster

The more molecular character of 9 in comparison to 8-gallium is responsible for a decrease of the bond lengths by about 25 pm. These results prove that 9, considering its synthesis as well as the electronic structure, has to be classified in between polyhedral gallium clusters such as the square antiprismatic cluster GajjiCnHcih2- 72 and metalloid clusters. 

The extraordinary bonding properties in 16 can also be seen in a diagram of 16 (Fig. 34). In 16, an almost perfect five-numbered axis is attained, distorted only by the central Ga2 unit. This is the first time that a symmetry close to the five-numbered symmetry is observed for molecular metalloid clusters. A few solid-state modifications with five-numbered symmetry have, however, been found for compounds involving Group 13 elements. Because there is no crystallographic space group with a five-numbered axis, these compounds are summarized under the collective name quasi-crystals .83 For a better understanding of quasi-crystals,... 

The clusters described so far have in common, that the number of metal atoms is less or equal than the number of substituents. However, there is a still growing number of both neutral and anionic clusters in which the number of metal atoms is larger than the number of substituents. As a consequence, these metal-rich clusters contain naked metal centers which are only bonded to other metal centers. Schnockel referred these ones to as metalloid clusters. Several metalloid A1 and Ga clusters were prepared by standard salt elimination reactions using metastable solutions of metal subhalides MX (M = Al, Ga X = Cl, Br) as well as solutions of Gal. Since the metal subhalides were found to play the key role for the successful synthesis of this particular class of compounds, they will be discussed first. (For excellent review articles see Refs 273 and 274.)... 

Metastable solutions of GaX (X = C1, Br) as well as conventionally prepared Gal react with lithium or sodium organometallics in standard salt metathesis reactions with formation of M2R4 (Section 3.07.4.1) as well as neutral and anionic clusters of the type MnRm]x m > n) (chapter 4.1). Moreover, metalloid clusters [MnRm]x (m < n), which feature different types of metallic core structures, have been obtained. Their formation strongly depends on the reaction conditions, in particular the reaction temperature, and the (donor) solvent. 

A metal atom cluster as defined by Cotton [1] is still a very broad term, because non-metal atoms can also be part of the cluster core. In this chapter mainly two types of metal atom clusters are presented the polyborane analogous polyhedral and the metalloid clusters E Rr of group 13 elements E. The structures and bonding of the polyhedral clusters with n < r are similar to those in the well-known polyboranes. 

In a metalloid cluster [2] more metal-metal bonds than metal-ligand bonds are involved, which means n > r. The largest structurally characterized compounds of this type contain 77 A1 or 84 Ga atoms, respectively [3, 4], Metal-metal bonds dominate these clusters and the framework of the resulting metal-metal bonds exhibits a geometry similar to the bulk metal itself. With respect to the Greek word ei8o< (idea, prototype) the suffix -oid indicates that the bulk metal element is actually visible in the metal atom core of the metalloid or more generally, elementoid clusters. 

We will first comment on metal-metal bonds (see Section 2.3.2) and then discuss (see Section 2.3.3) the polyhedral clusters [6], followed by the second central subject, the metalloid clusters in Section 2.3.4 (for recently published reviews see e.g., Refs. [7-11]). 

This section will focus on homonuclear neutral or anionic clusters of the elements aluminum, gallium, indium, and thallium, which have an equal number of cluster atoms and substituents. Thus, they may clearly be distinguished from the metalloid clusters described below, which in some cases have structures closely related to the allotropes of the elements and in which the number of the cluster atoms exceeds the number of substituents. The compounds described here possess only a single non-centered shell of metal atoms. With few exceptions, their structures resemble those of the well-known deltahedral boron compounds such as B4(CMe3)4 [30], B9CI9 [31] or [B H ]2 [32]. The oxidation numbers of the elements in these... 

However, mixtures of these products with some gallium rich metalloid clusters were formed so that this method is rather inadequate, and compounds 10-12 were isolated in very low yields. 

Since the large majority of metalloid clusters E Rthis section is divided in two parts, including the few clusters for In hitherto known. For many of the metalloid clusters discussed in this section (for a definition of metalloid cf. Section 2.3.1, Introduction) the technique of cryochemistry is essential, i.e., trapping of a high-temperature species together with an excess of a suitable solvent in order to obtain a metastable solution. Detailed descriptions and discussions of this technique have been presented recently [7-12],... 

The principle and the significance of metalloid clusters for the understanding of the formation of metals are made clear by the two largest A1 clusters 61 and 63, which have almost the same size as the 69 and 77 A1 atoms and 18 and 20 N(SiMe3) groups [3, 91]. In both cases the A1 atoms are arranged in shells (Fig-... 

Fig. 2.3-14. Arrangement of the Al atoms in the metalloid clusters 61 and 63 in a stick-and-ball and a shell-like representation with different colors for the different shells 61 (1 +12 + 38 + 18 Al atoms) 63 (1 +12 + 44 + 20 Al...

Fig. 2.3-23. Molecular structure of 76b (only the Si atoms directly bonded to the Ga atoms are shown) and of the metalloid cluster 77.

Despite this, proven rules for boron clusters can be applied to the smaller metalloid Al, Ga, and In clusters with certain additional assumptions, as recent DFT calculations have shown [87]. In addition, counting rules for smaller Ga and Al metalloid clusters have been developed [123], which will, however, probably not be transferable to the larger clusters. Therefore the first assignment principle presented here for the larger metalloid clusters incorporates the structures of the elements in the various modifications, which means that the metalloid or elementoid clusters are described as nanostructured element modifications. 

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