Carborane cluster systems

This review will restrict itself to boron-carbon multiple bonding in carbon-rich systems, as encountered in organic chemistry, and leave the clusters of carboranes rich in boron to the proper purview of the inorganic chemist. Insofar as such three-dimensional clusters are considered at all in these review, interest will focus on the carbon-rich carboranes and the effect of ring size and substituents, both on boron and carbon, in determining the point of equilibrium between the cyclic organoborane and the isomeric carborane cluster. A typical significant example would be the potential interconversion of the l,4-dibora-2,5-cyclohexadiene system (7) and the 2,3,4,5-tetracarbahexaborane(6) system (8) as a function of substituents R (Eq. 2). 

L Monomeric and Polymeric Organic Analogs of Boron Cluster Systems The polyhedral clusters of boranes and carboranes are groups of cluster systems that are present ubiquitously in organoboron polymers. As in the case with the... 

Molecular structures of some hypho cluster systems (a) B5H9(PMe3)2 (b) (NCCH2)C3B6Hj 2 (c) [/u,2- C(CN)2 2]C2B7H12. In carboranes (b) and (c), for clarity only bridging and extra H atoms are included, and all exo H atoms attached to the vertices are omitted. 

The neutral chloride B4CLt, with four skeletal bond pairs, and tetrahedrane C4H4 or tetraphosphorus P4 and related molecules, with six skeletal bond pairs, are systems with regular tetrahedral structures. Tetrahedral molecules held together by six skeletal bond pairs can of course be accommodated in the carborane cluster systematics as nido clusters with n atoms and n -1- 2 skeletal bond pairs, if a low connectivity (axial) vertex of the parent trigonal bipyramid is left vacant, instead of the expected high-connectivity (equatorial) vertex. 

The metal-carbon cluster systems we have considered so far in the present chapter, like the carboranes considered in the previous chapter, have contained one or more skeletal carbon atoms occupying vertex sites on the cluster deltahedron or deltahedral fragment. We now turn to some molecular cluster systems in which hypercoordinated carbon atoms occupy core sites in the middle of metal polyhedra. Most are metal carbonyl carbide clusters of typical formulae Mj (CO)yC. Their carbide carbon atoms are incorporated within polyhedra, which in turn are surrounded by y carbonyl ligands. Such compounds, for which few controlled syntheses are available, have been found primarily among the products of thermal decomposition of polynuclear metal carbonyls Mj (CO)j, their carbide carbon atoms result from disproportionation reactions of carbonyl ligands (2 CO CO2 + C). 

Recent research activity in carborane chemistry has been directed toward expanding the use of carborane clusters in materials science including, among others, molecular recognition systems, display devices, modular construction systems, NLO materials and special polymers. Nonetheless, their use in developing functional materials such as olefin polymerization catalysts and luminescent materials is still limited. 

The supramolecular chemistry of carborane clusters received significant impulses in the 1990s with the development of two types of compounds the arene-coupled macrocyclic systems incorporating ctoio-carboranes, and the mercuracarborands. 

For compounds to be useful in BNCT, they must allow administration to a patient (usually through the blood stream), accumulate or be retained in the tumor, be of low toxicity, and on the basis of the required accumulation, carry as many boron atoms as possible. To achieve the latter, boron clusters are of great value. In this chapter, the chemistry of some clusters is described that have found application in BNCT (see Scheme 2.2-1). The focus is on the o-carborane system dicarba-doso-dodecaborane, C2B1oH12, and its degradation product nido-carborate,... 

The electron counting rules of Wade (S3), Williams (117), and Rudolph (118) can serve as a useful concept to explain structure and bonding in a variety of systems which at first glance are very different Zintl phases, boranes and carboranes, transition metal n complexes and carbonyl clusters, nonclassical carbocations, and also n complexes of main-group elements. According to... 

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