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Concept
Boranes
Summary
A borane is a compound with the formula BxHy or a related anion. Many such boranes are known. Most common are those with 1 to 12 boron atoms. Although they have few practical applications, the boranes exhibit structures and bonding that differs strongly from the patterns seen in hydrocarbons. Hybrids of boranes and hydrocarbons, the carboranes are also well developed.
The development of the chemistry of boranes led to innovations in synthetic methods as well as structure and bonding. First, new synthetic techniques were required to handle diborane and many of its derivatives, which are both pyrophoric and volatile. Alfred Stock invented the glass vacuum line for this purpose.
The structure of diborane was correctly predicted in 1943 many years after its discovery. The structures of the boron hydride clusters were determined beginning in 1948 with the characterization of decaborane. William Lipscomb was awarded the Nobel prize in Chemistry in 1976 for this and many subsequent crystallographic investigations. These investigations revealed the prevalence of deltahedral structures, i.e., networks of triangular arrays of BH centers.
The bonding of the clusters ushered in Polyhedral skeletal electron pair theory and Wade's rules, which can be used to predict the structures of boranes. These rules were found to describe structures of many cluster compounds.
Interest in boranes increased during World War II due to the potential of uranium borohydride for enrichment of the uranium isotopes and as a source of hydrogen for inflating weather balloons. In the US, a team led by Schlesinger developed the basic chemistry of the anionic boron hydrides and the related aluminium hydrides. Schlesinger's work laid the foundation for a host of boron hydride reagents for organic synthesis, most of which were developed by his student Herbert C. Brown. Borane-based reagents are now widely used in organic synthesis. Brown was awarded the Nobel prize in Chemistry in 1979 for this work.
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