Intermetalloid cluster

Wang JQ, Stegmaier S, Fassler TF (2009) [Co Geio] An intermetalloid cluster with archimedean pentagonal prismatic stmcture. Angew Chem Int Ed 48 1998-2002... 

Relationships Between Soluble Zintl Anions, Ligand-Stabilized Cage Compounds, and Intermetalloid Clusters of Tetrel (Si-Pb) and Pentel (P-Bi) Elements... 

Zintl Anions, Ligand-Stabilized Cage Compounds, and Intermetalloid Clusters of the... 

Fig. 1 Examples of polyhedral cage molecules and metalloid clusters (first row) compared to related Zintl ions and intermetalloid clusters that are obtained from the reaction of Zintl ions (second row)...

In this chapter, the chemistry and the structures of Zintl ions and cage molecules are summarized and put in the context of intermetalloid clusters. The emphasis is put on the observation that irrespective of the starting material (Zintl ions or small low-valent organometallic compounds) the same types of intermetalloid clusters are formed. 

In summary, the bonding situation found in the deltahedral stmctures of bare Zintl ions, which follow Wade s mles, changes smoothly to that observed in ligand-stabilized metalloid and heteroatomic clusters. Therefore, they can be considered as a subclass of intermetalloid clusters. The accessibility of larger intermetalloid... 

The first example of an intermetalloid cluster that almagamates 11 Bi and 9 Zn atoms has been found in the complex [K(2.2.2-crypt)]5[Zn9Bin]-2en-toluene (2.2.2-crypt = 4,7,13,16,21,24-hexaoxa-l,10-diazabicyclo[8.8.8] hexacosane). The naked [Zn ZngBi4 Bi7]5 cluster consists of a central Zn atom trapped inside a distorted icosahedron whose vertices are 8 Zn atoms and 4 Bi atoms, with 7 of the 20 triangular faces each capped by a Bi atom, as shown in Fig. 15.6.3(b). 

This chapter reviews the synthesis, structures and physical properties of homoatomic Zintl ions and recent developments in the formation of mixed clusters consisting of the tetrel elements Ge, Sn, and Pb and various d-block elements. A brief summary is provided of the chemistry of homoatomic clusters (this has been reviewed earlier [1,2]), with the main focus being oriented towards the latest results in the field of intermetalloid clusters [3, 4]... 

The intermetalloid cluster [Ni3 Gei8]" displayed a somewhat similar structure, where a linear trimer of Ni atoms was found to bind to two separated, widely opened Geg clusters [66]. These two Geg units featured the same shape as that of the two Eg subunits found in [Pd2 Eig]". Although the Ge atoms of the two cluster units are not connected, the relative orientation of the atoms of each open face is already staggered, as it is required for an 18-vertices cage [79]. 

The bottom-up synthesis of well-defined (semi)metal and intermetalloid clusters that can reach the nanometer scale represents a major challenge. Deltahedral structures reach a limit in size unless more capable templates are found. However, Zintl ions themselves can serve as building units for the formation of larger structures, including classical and nonclassical tetrel-tetrel bonds. Two further examples justify the plan to use such tetrel dusters as precursors for nanoscale dusters ... 

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