clusters Dicarbaboranes can be prepared from boron hydrides using alkynes as the source of the two carbon centers. In addition to the closo-C2BnHn+2 series mentioned above, several open-cage dicarbon species are known including nido-C2B3H7 (isostructural and isoelectronic with B5H9) and arachno-C2B7H13. Syntheses of icosahedral closo-dicarbadodecaborane derivatives (R2C2B10H10) employ alkynes as the R2C2 source and decaborane (B10H14) to supply the B10 unit. Classification by cage size The following classification is adapted from Grimes's book on carboranes. Small, open carboranes This family of clusters includes the nido cages CB5H9, C2B4H8, C3B3H7, C4B2H6, and C2B3H7. Relatively little work has been devoted to these compounds. Pentaborane[9] reacts with acetylene to give nido-1,2-C2B4H8. Upon treatment with sodium hydride, latter forms the salt Na[1,2-C2B4H7]. Small, closed carboranes This family of clusters includes the closo cages C2B3H5, C2B4H6, C2B5H7, and CB5H7. This family of clusters are also lightly studied owing to synthetic difficulties. Also reflecting synthetic challenges, many of these compounds are best known as their alkyl derivatives. 1,5-C2B3H5 is the only known isomer of this five-vertex cage. Intermediate-sized carboranes This family of clusters includes the closo cages C2B6H8, C2B7H9, C2B8H10, and C2B9H11. Isomerism is well established in this family: 1,2- and 1,6-C2B6H8, and 2,3- and 2,4-C2B5H7, as well as in open-cage carboranes such as 2,3- and 2,4-C2B4H8 and 1,2 and 1,3-C2B9H13. In general, isomers having non-adjacent cage carbon atoms are more thermally stable than those with adjacent carbons, so that heating tends to induce mutual separation of the carbon atoms in the framework. Carboranes of intermediate nuclearity are most efficiently generated by degradations starting with carborane as summarized in these equations, starting from C2B9H12−: C2B9H12− + H+ → C2B9H13 C2B9H13 → C2B9H11 + H2 In contrast, smaller carboranes are usually prepared by building-up routes, e.g. from pentaborane + alkyne. Chromate oxidation of this 11-vertex cluster results in deboronation, giving C2B7H13. From that species, other clusters result by pyrolysis, sometimes in the presence of diborane: C2B6H8, C2B8H10, and C2B7H9. Icosahedral carboranes The icosahedral charge-neutral closo-carboranes, 1,2-, 1,7-, and 1,12- C2B10H12 (informally ortho-, meta-, and para-carborane) are particularly stable and are commercially available. The ortho-carborane forms first upon the reaction of decarborane and acetylene. It converts quantitatively to the meta-carborane upon heating in an inert atmosphere. Producing meta-carborane from ortho-carborane requires 700 °C, proceeding in ca. 25% yield. [CB11H12]− is also well established. Reactions Base-induced degradation of carboranes give anionic nido derivatives, which can be employed as ligands