Metal clusters chemical bonding

Keywords Adaptive natural density partitioning All transition metal aromaticity Chemical bonding Cluster Multifold aromaticity... 

Clusters are intennediates bridging the properties of the atoms and the bulk. They can be viewed as novel molecules, but different from ordinary molecules, in that they can have various compositions and multiple shapes. Bare clusters are usually quite reactive and unstable against aggregation and have to be studied in vacuum or inert matrices. Interest in clusters comes from a wide range of fields. Clusters are used as models to investigate surface and bulk properties [2]. Since most catalysts are dispersed metal particles [3], isolated clusters provide ideal systems to understand catalytic mechanisms. The versatility of their shapes and compositions make clusters novel molecular systems to extend our concept of chemical bonding, stmcture and dynamics. Stable clusters or passivated clusters can be used as building blocks for new materials or new electronic devices [4] and this aspect has now led to a whole new direction of research into nanoparticles and quantum dots (see chapter C2.17). As the size of electronic devices approaches ever smaller dimensions [5], the new chemical and physical properties of clusters will be relevant to the future of the electronics industry. 

The validity (or lack thereof) of the classical Zind formahsm as applied to less polar intermetallics, involving metals along the Zind border, is nicely probed by electron-poof trelides. Seminal work by Corbett [44] and Belin [48] recognized the proclivity of trelides (Ga, In, H) to form cluster-based anion structures. The apparent electron deficiency in the chemical bonding of these cluster com-... 

The literature of metal-support interactions includes httle about the possible chemical bonding of metal clusters or particles to supports. Supported molecular metal clusters with carbonyl ligands removed have afforded opportunities to understand the metal-support interface in some detail, and the results provide insights into the bonding of clusters to supports that appear to be generalizable beyond the small clusters to the larger particles of conventional supported metal catalysts [6]. 

Colloidal systems of particles are different from molecular clusters in having a small distribution in sizes. Also, colloidal systems may be stabilized by organic molecules, resulting in chemical bonds between these and the outer monolayer of metal atoms. The Mossbauer study of such systems includes rather diverse fields ... 

Metal-metal (M-M) bonds, first noted in the early sixties, occur in several thousand transition-metal compounds [1]. Complex technetium compounds and compounds with M-M bonds (clusters) have been studied more extensively than many other classes of inorganic compounds. Increasing interest in technetium compounds is due to the practical uses of the "mTc isotope, which ranks first among radioactive isotopes used in nuclear medicine diagnostics [2-4]. On the other hand, technetium clusters are an interesting object for theoretical studies, because until recently, they were the only compounds in which the presence of these anomalous chemical bonds was thought possible. 

A structural classification of 8 is difficult due to the fact that an arrangement of metal atoms as in 8 is uncommon in the whole field of molecular metal clusters. For this reason, detailed understanding of the bonding properties in 8 requires quantum chemical calculations. Theoretical analysis seems to be especially applicable to learning more about the bond between the two tetrahedra, which appears at first to be an isolated metal-metal bond between two metal atoms in the formal oxidation state zero. 

Gas phase transition metal cluster chemistry lies along critical connecting paths between different fields of chemistry and physics. For example, from the physicist s point of view, studies of clusters as they grow into metals will present new tests of the theory of metals. Questions like How itinerant are the bonding electrons in these systems and Is there a metal to non-metal phase transition as a function of size are frequently addressed. On the other hand from a chemist point of view very similar questions are asked but using different terminology How localized is the surface chemical bond and What is the difference between surface chemistry and small cluster chemistry Cluster science is filling the void between these different perspectives with a new set of materials and measurements of physical and chemical properties. 

The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modem structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus... 

Here, as in other branches of inorganic chemistry, interatomic distances show a considerable variation and, although some correlation with bond order is possible, attempts to do so should be regarded with caution.For metals with close-packed structures, the coordination number of any atom is 12 for cubic or hexagonal structures, and 14 (8 plus 6 more neighbors at about 15% further away) for body-centered cubic structures. In general, this number exceeds the number of electrons per atom available for metal-metal bond formation and precludes the formation of localized, two-electron bonds between metal atoms. Bond orders of less than 1 are therefore commonly recorded. For metal clusters, it is necessary to consider the variety of ways in which valence electrons may be utilized in chemical bonding within the Mm... 

As mentioned in the Introduction, no structural information on these species was available for more than 40 years after the discovery of the first Zintl metal cluster anions, since no pure crystalline phases could be isolated and characterized structurally. Nevertheless, early efforts to rationalize the observed formulas and chemical bonding of these intermetallics and related molecules utilized the Zintl-Klemm concept [75, 76] and the Mooser-Pearson [77] extended (8 — N) rule. In this rule N refers to the number of valence electrons of the more electronegative metal (and thus anionic metal) in the intermetallic phases. 

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