The cobalt bis(dicarbollide)(1-) anion (1-), [(1,2-C2B9H11)2-3,3'-Co(III)](1-), plays an increasingly important role in material science and medicine due to its high chemical stability, 3D shape, aromaticity, diamagnetic character, ability to penetrate cells, and low cytotoxicity. A key factor enabling the incorporation of this ion into larger organic molecules, biomolecules, and materials, as well as its capacity for "tuning" interactions with therapeutic targets, is the availability of synthetic routes that enable easy modifications with a wide selection of functional groups. Regarding the modification of the dicarbollide cage, syntheses leading to substitutions on boron atoms are better established. These methods primarily involve ring cleavage of the ether rings in species containing an oxonium oxygen atom connected to the B(8) site. These pathways are accessible with a broad range of nucleophiles. In contrast, the chemistry on carbon vertices has remained less elaborated over the previous decades due to a lack of reliable methods that permit direct and straightforward cage modifications. In this review, we present a survey of methods based on metalation reactions on the acidic C-H vertices, followed by reactions with electrophiles, which have gained importance in only the last decade. These methods now represent the primary trends in the modifications of cage carbon atoms. We discuss the scope of currently available approaches, along with the stereochemistry of reactions, chirality of some products, available types of functional groups, and their applications in designing unconventional drugs. This content is complemented with a report of the progress in physicochemical and biological studies on the parent cobalt bis(dicarbollide) ion and also includes an overview of recent syntheses and emerging applications of boron-substituted compounds.

• Keywords
• borane, carborane, cobalt bis(dicarbollide), dicarbollide, lithiation, metalation,
• Publication type
• Journal Article MeSH
• Review MeSH

A small library of boron-cluster- and metallacarborane-cluster-based ligands was designed, prepared, and tested for isoform-selective activation or inhibition of the three nitric oxide synthase isoforms. On the basis of the concept of creating a hydrophobic analogue of a natural substrate, a stable and nontoxic basic boron cluster system, previously used for boron neutron capture therapy, was modified by the addition of positively charged moieties to its periphery, providing hydrophobic and nonclassical hydrogen bonding interactions with the protein. Several of these compounds show efficacy for inhibition of NO synthesis with differential effects on the various nitric oxide synthase isoforms.

• MeSH
• Models, Chemical MeSH
• Cobalt chemistry   MeSH
• Humans MeSH
• Molecular Structure MeSH
• Organometallic Compounds chemical synthesis   pharmacology   MeSH
• Protein Isoforms MeSH
• Boron Compounds chemical synthesis   pharmacology   MeSH
• Nitric Oxide Synthase antagonists & inhibitors   metabolism   MeSH
• Check Tag
• Humans MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Research Support, N.I.H., Extramural MeSH
• Names of Substances
• Cobalt MeSH
• Organometallic Compounds MeSH
• Protein Isoforms MeSH
• Boron Compounds MeSH
• Nitric Oxide Synthase MeSH