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Carborane

physical science Maturity 9-11 Next article →

Carboranes are unique chemical clusters made of boron, carbon, and hydrogen atoms. They belong to a group called heteroboranes, which are clusters containing different types of atoms. Unlike many organic compounds that form simple chains or rings, carboranes build three-dimensional cage structures. These cages are held together by electron-delocalized bonding. This means the electrons are shared across the entire cluster rather than being stuck between just two atoms.

O-carborane-3D-balls
O-carborane-3D-balls

This shared bonding allows the atoms to form complex, stable polyhedra.

To understand these shapes, scientists use the Wade–Mingos rules. Kenneth Wade first proposed these rules in 1971, and Michael Mingos expanded them in 1972. These rules explain how the multi-centered bonding works between boron, carbon, and hydrogen. The rules help predict the geometry of the cluster based on how many electrons are available. The clusters are categorized by how complete their polyhedral shapes are. A complete shape is called a closo- cluster. If the shape is missing vertices, it receives different names. For example, a nido- cluster is missing one vertex, while an arachno- cluster is missing two. Other types include hypho-, hypercloso-, iso-, klado-, conjuncto-, and megalo- clusters.

Carboranes vary significantly in size. The cage framework can contain as few as 5 atoms or as many as 14 atoms. Most carboranes feature two carbon atoms within the cage. These are often called dicarbaboranes. Some clusters, known as monocarboranes, contain only one carbon atom. These are often made by adding one-carbon reagents like formaldehyde, cyanide, or isocyanides to boron hydride clusters. For instance, monocarbadodecaborate is produced using decaborane and formaldehyde, followed by the addition of borane dimethylsulfide.

1,3-C2B7H13
1,3-C2B7H13

There are different ways to prepare these clusters depending on their size. Smaller carboranes are usually built up from smaller parts. For example, pentaborane can react with acetylene to create nido-1,2-carborane. Larger, intermediate-sized clusters are often made by degrading larger clusters into smaller ones. One method involves the chromate oxidation of 11-vertex clusters. This process causes deboronation, which removes a boron atom. The resulting species can then be manipulated through heating, or thermolysis, to create new clusters.

CAHBOR01
CAHBOR01

Isomerism is a key feature of carborane structure. Geometrical isomers occur based on where the carbon atoms are located in the cage. In the 12-vertex closo-dicarbadodecaborane family, three specific isomers exist: 1,2-, 1,7-, and 1,12-. These are often called ortho-, meta-, and para-carborane. The 1,2- isomer, or ortho-carborane, is usually the first to form when decaborane reacts with acetylene. If you heat ortho-carborane to 700 °C in an inert atmosphere, it converts into meta-carborane. This process typically has a yield of about 25%. Generally, isomers where the carbon atoms are not next to each other are more thermally stable.

Carboranes also interact with metals to form new structures. Through a process called metalation, carboranes can react with iron carbonyl sources. Base-induced degradation can also create anionic nido-derivatives. These can act as ligands, which are molecules that attach to metals. This creates metallacarboranes, which contain transition metals or main group metals within the cage framework. The most famous of these are dicarbollide complexes.

Carborane-acid-3D-balls
Carborane-acid-3D-balls

Research into carboranes has led to several significant applications. In environmental science, bis(dicarbollide) has been used as a precipitant to help remove radiowastes. In medicine, carboranes are being explored for boron neutron capture therapy. This uses the boron within the carborane to help treat certain conditions. Additionally, carborane acid is a powerful superacid. It is strong enough to protonate fullerene. This makes carboranes a vital subject in the study of both highly reactive acids and specialized medical technologies.

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File:Carborane-acid-3D-balls.png
Carborane-acid-3D-balls.png
File:CAHBOR01.png
CAHBOR01.png
File:1,3-C2B7H13.svg
1,3-C2B7H13.svg
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