Metal polyhedral clusters

So far, three types of i-QCs appear in the literature Mackay [17], Bergman [18], and Tsai types [19], which have been differentiated on the basis of the polyhedral cluster sequences observed in the respective 1/1 AC structures. These are commonly represented as shown in Fig. 2. An i-QC is concluded to be Mackay-type if its 1/1 AC contains a 54-atom multiply endohedral cluster ordered, from the center out, as a small icosahedron (12 atoms), a larger icosahedron (12), and an icosidodecahe-dron (30). This motif occurs in ACs that consist of transition metals and main-group elements on the right side of the periodic table such as Al-(Pd,Mn)-Si [17,20]. In... 

More often, polyhedral clusters with strong metal-metal (or metalloid-metalloid) bonding are the major structural motifs of classic Zintl phases. These are nominally salts composed of reduced p- (i.e., post-transition) elements that are usually inter-bonded into closed shell polyanions plus active metal cations, originally the alkali... 

Rules for counting the number of skeletal electrons provided by each vertex atom need to be established in order to determine the number of skeletal electrons in polygonal and polyhedral clusters of the post-transition elements. The rules discussed above for polyhedral boranes can be adapted to bare post-transition metal vertices as follows ... 

Bare group 13 metal vertices (e.g., Ga, In, Tl) provide, as noted above, only one skeletal electron each to polyhedral cluster structures. Thus it is not surprising that the bare metal cluster ions Enz (E = group 13 element) found in homonuclear alkali-metal/group 13 intermetallic phases [86-89] (mainly for In and Tl) have charges less negative than the — (n + 2) (i.e., z [Pg.21]

Another very useful rule for classifying the structures of polyboranes and hetero-boranes as well as many metal boron cluster compounds and their derivatives has been developed by Rudolph, Williams, Mingos and Wade (see Chapter 1.1.2) [4]. Today these are generally termed the Wade rules. They can be derived from the structures and electronic requirements of closed polyhedral boranes, such as an octahedron or an icosahedron, which are present in the anions B6H62 and B,2 H, 22. Since there are only exopolyhedral B-H bonds the number of electron... 

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. 

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]). 

Metal atoms have fewer valence electrons than orbitals available for bonding and in this they resemble boron. The consequences of this idea are examined and it is shown that many metals with electronegativities in the range 1.6-2.4 (B = 2.0) can subrogate boron atoms as vertices in polyhedral clusters. Such metalloboranes are often much more stable than the parent boranes or borane anions. Not only can metals mimic boron in known cluster geometries but the flexibility thus introduced can lead to novel and previously unsuspected cluster geometries. The construction of macropolyhedral clusters containing 17-20 vertices is also described. 

Some c/o o-Mbtallo-boranbs and -carboranes Containing at Least 1 Metal Atom in the n-VBRTEX Polyhedral Cluster... 

The geometries of metal carbonyl and metallocarborane cluster compounds have been systematized recently by a set of simple rules described collectively as the polyhedral skeletal electron pair theory (153, 218, 232). This approach originated from a perceptive analogy between isostructural metal carbonyl and borane polyhedral cluster molecules (232), and its applications have been widely discussed and reviewed (147, 153, 210, 218, 233, 234, 235, 240). In this review,... 

Definitions of a metal atom cluster compound have been given (109, 233, 241, 316). Accordingly, in this review a cluster will be considered as a compound containing at least three metal atoms connected by metal-metal interactions in a triangular or polyhedral array. 

Another class of molecules that will be discussed contains cluster compounds such as the polyhedral borane anions, B H -", and some metal containing species such as the metal carbonyl clusters. 

Much of the current literature on metal atom cluster species employs bonding concepts that are derived from MO treatment of the polyhedral borane anions, We thus begin by discussing these species, of which the most important examples are shown in Figure 8.15. We shall deal with the BaHg" ion in detail to illustrate the general approach to these systems. 

For polyhedral clusters (sometimes called deltahedral, because the faces are all triangles resembling the Greek letter delta) the ancestor of all electron counting schemes is the correlation proposed by Wade between borane (or carborane) cages and metal carbonyl cages. Wade first drew attention to the similarity of a M(CO)3 unit and a BH (or CH) unit, a relationship that we would now call isolobality (Section 1-6). He then proposed that the 2n + 2 rule for closo boranes (Chapter 5) would also apply to closo metal cluster species such as [Os CO) ]2, and that 2n + 4 and 2n + 6 electron counts would, similarly, be appropriate for stable M clusters with nido and arachno structures. Hydrogen atoms are assumed to contribute one electron each, an interstitial carbon atom four electrons, and so on. 

Let us now ask how we could predict the correct total electron count, as just defined, for a stable cluster of known structure (i.e., closo, nido, or arachno). To do this for metal carbonyl clusters, it is postulated that in addition to the electrons necessary for skeletal bonding each metal atom will also have 12 nonskeletal electrons. The basis for this assumption is that in the pyramidal M(CO)3 unit each M—CO bond will comprise two formally carbon tr electrons that are donated to the metal atom and two formally metal it electrons that backbond, at least partially, to the CO ligand. Thus, in predicting the total electron count for a closo polyhedral cluster of n vertices, the result would be 12n + 2 n + 1). Similarly, for nido and arachno clusters that are derived from an n-vertex polyhedron (their parent polyhedron) by removal of one or two vertices, respectively, there will be 12 and 24 fewer total electrons, respectively. 

Metallacarbaborane (also called metallacarborane) an electron-deficient compound, usually a polyhedral cluster comprising an array of boron-hydride (BH), carbon-hydride (CH), and metal (ML, where L = ligand) fragments the inclusion of a substituted carbon fragment CR (R = alkyl, aryl, or trimethylsilyl) in place of a CH unit is common... 

In almost all metallacarbaboranes, the total number of B and C atoms in the polyhedral cluster exceeds the number of metal atoms. A rare example of a metal-rich metaUacarbaborane is c/oio-Fe3(CO)9BHCHCMe (32) the complex has also been described in terms of an -borirene ligand coordinating to an Fc3 unit. ... 

---