Clusters Including Halogen Atoms

5- 13) remains monomeric even in the solid state with coordinatively unsaturated gallium atoms [88]. The preference of the monomeric structure in that case may be caused by the relatively small covalent radius of the gallium atoms and the strong repulsion between the bulky C(SiMe3)3 substituents [89]. 

The only thallium compound to be discussed here is the Tlf,Cl2[Si(CMe3)3]6 cluster 61. This remarkable compound was formed by the reaction of thallium) 111) chloride with NaSi(CMe3)3 [Eq. (28)] and precipitated in the form of black crystals in 21% yield, when a solution in toluene was stored at —25 °C for six months [92], Solutions of 61 in benzene decompose slowly at room temperature by the formation of ClSi(CMe3)3 and a black, not identified precipitate. The structure of 61 consists of two four-membered T13C1 heterocycles, which are connected by one Tl-Tl and two Tl-Cl bonds. A monomeric TI3CI heterocycle was isolated as a byproduct in which one thallium atom was bonded to two Si(CMe3)3 substituents. 

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Derivatives of the boranes include not only simple substituted compounds in which H has been replaced by halogen, OH, alkyl or aryl groups, etc., but also the much more diverse and numerous class of compounds in which one or more B atom in the cluster is replaced by another main-group element such as C, P or S, or by a wide range of metal atoms or coordinated metal groups. These will be considered in later sections. 

After the brief introduction to the modem methods of ab initio quantum chemistry, we will discuss specific applications. First of all, we will discuss some general aspects of the adsorption of atoms and molecules on electrochemical surfaces, including a discussion of the two different types of geometrical models that may be used to study surfaces, i. e. clusters and slabs, and how to model the effect of the electrode potential in an ab initio calculation. As a first application, the adsorption of halogens and halides on metal surfaces, a problem very central to interfacial electrochemistry, will be dealt with, followed by a section on the ab initio quantum chemical description of the adsorption of a paradigmatic probe molecule in both interfacial electrochemistry and surface science, namely carbon monoxide. Next we will discuss in detail an issue uniquely specific to electrochemistry, namely the effect of the electric field, i. e. the variable electrode potential, on the adsorption energy and vibrational properties of chemisorbed atoms and molecules. The potential-dependent adsorption of carbon monoxide will be discussed in a separate section, as this is a much studied system both in experimental electrochemistry and ab initio quantum electrochemistry. The interaction of water and water dissociation products with metal surfaces will be the next topic of interest. Finally, as a last... 

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