Arachno Carboranes species

As with the simple boranes, the closo carboranes are generally more thermally stable than the corresponding nido and arachno species. Thermal decomposition of nido and arachno carboranes often leads to one or more closo carborane. For example, pyrolysis of 2,3-C2B4Hg is another route to 2,3-C2B3H2 [30347-95-6], l,2-C2B4Hg [20693-68-9] and l,6-C2B4Hg [20693-67-8], and 1,5-C2B3H3 [20693-66-7] (123). 

Recent synthetic studies have shown that carborane skeletons larger than the icosahedron can be constructed by the insertion of additional BH units. The reaction scheme and structure motifs of these carborane species are shown in Fig. 13.4.15. Treatment of 1,2-(CH2)3-1,2-C2BioHio (1) with excess lithium metal in THF at room temperature gave [(CH2)3-l,2-C2BioHio][Li4(THF)s] 2 (2) in 85% yield. X-ray analysis showed that, in the crystalline state, both the hexagonal and pentagonal faces of the carbon-atoms-adjacent arachno-carborane tetra-anion in 2 are capped by lithium ions, which may in principle be substituted by BH groups. 

Wade also incorporates electron-rich species such as C5H5 and C4H42- as arachno species derived by removal of two nonadjacent high-coordination vertices from the pentagonal and tetragonal bipyramids, respectively, and has, moreover, correlated many aspects of seemingly unrelated classes of compounds beyond the recognized borders of carborane chemistry. 

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. 

The structural patterns illustrated in Figure 3.1, and the shapes shown in column 3 for arachno species, are essentially those first suggested by Williams in 1971,2 and have stood the test of time remarkably well. However, the shapes shown should be regarded as illustrative rather than definitive. As with the nido species, alternative shapes to those shown in Figure 3.1 are possible for arachno species, with different sites left vacant on the parent deltahedron. We have already noted that many nido boranes and carboranes with eight skeletal atoms show deviations in their atom connectivities from those shown in Figure Nevertheless, apart from these particular exceptions,... 

To underline the structural and bonding relationship between these mixed metal-carbon cluster species and carboranes, we list the formulae of representative examples in Table 4.1, classified according to the numbers of skeletal bonding electrons they contain and thus according to their structural type (closo, nido, or arachno ). 

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