BH3 dimerises to diborane, B2H6.

In chemistry, a borane is a chemical compound of boron and hydrogen. The boranes comprise a
large group of compounds with the generic formulae of BxHy. These compounds do not occur in
nature. Many of the boranes readily oxidise on contact with air, some violently. The parent
member BH3 is called borane, but it is known only in the gaseous state, and dimerises to form
diborane, B2H6. The larger boranes all consist of boron clusters that are polyhedral, some of
which exist as isomers. For example, isomers of B20H26 are based on the fusion of two 10-atom
clusters.

The most important boranes are diborane B2H6, pentaborane B5H9, and decaborane B10H14.
The development of the chemistry of boron hydrides led to new experimental techniques and
theoretical concepts. Boron hydrides have been studied as potential fuels, for rockets and for
automotive uses.

Over the past several decades, the scope of boron hydride chemistry has grown to include cages
containing atoms other than boron, such as carbon in the carboranes and metals in the
metallaboranes, wherein one or more boron atoms are substituted by metal atoms.

Generic formula of boranes

The four series of single-cluster boranes have the following general formulae, where "n" is the
number of boron atoms:

Type formula notes

2−
closo− BnHn No neutral BnHn+2 boranes are known
nido− BnHn+4
arachno− BnHn+6
hypho− BnHn+8 only adducts established

There also exists a series of substituted neutral hypercloso-boranes that have the theoretical
formulae BnHn. Examples include B12(OCH2Ph)12, which is a stable derivative of hypercloso-
B12H12[1].
Naming conventions
The naming of neutral boranes is illustrated by the following examples, where the Greek prefix
shows the number of boron atoms and the number of hydrogen atoms is in brackets:

 B5H9 pentaborane(9)
 B6H12 hexaborane(12)

The naming of anions is illustrated by the following, where the hydrogen count is specified first
followed by the boron count, and finally the overall charge in brackets:

 B5H8− octahydropentaborate(1−)

Optionally closo− nido− etc (see above) can be added:-

 B5H9, nido−pentaborane(9)
 B4H10, arachno−tetraborane(10)
 B6H62−, hexahydro−closo−hexaborate(2−)

Understandably many of the compounds have abbreviated common names.

Cluster types
It was realised in the early 1970s that the geometry of boron clusters are related and that they
approximate to deltahedra or to deltahedra with one or more vertices missing. The deltahedra
that are found in borane chemistry are (using the names favoured by most chemists)

deltahedron vertices
Trigonal bipyramid 5
Octahedron 6
Pentagonal bipyramid 7
Dodecahedron (see Snub disphenoid) 8
Tricapped trigonal prism 9
Bicapped square antiprism 10
Octadecahedron 11
Icosahedron 12
One feature of these deltahedra is that boron atoms at the vertices may have different numbers of
boron atoms as near neighbours. For example, in the pentagonal bipyramid, 2 borons have 3
neighbors, 3 have 4 neighbours, whereas in the octahedral cluster all vertices are the same, each
boron having 4 neighbours.

Diborane, B2H6
Pentaborane-[9], B5H9 Decaborane-[14], B10H14
B H 2-
12 12

B6H10 is a typical example. Its geometry is, in essence, a 7-boron framework (pentagonal
bipyramid), missing a vertex that had the highest number of near neighbours, e.g., a vertex with
5 neighbours. The extra hydrogen atoms bridge around the open face. A notable exception to this
general scheme is that of B8H12, which would be expected to have a nido- geometry (based on
B9H92− missing 1 vertex), but is similar in geometry to B8H14, which is based on B10H102−.

The names for the series of boranes are derived from this general scheme for the cluster
geometries:-

 hypercloso- (from the Greek for "over cage") a closed complete cluster, e.g., B8Cl8 is a
slightly distorted dodecahedron
 closo- (from the Greek for "cage") a closed complete cluster, e.g., icosahedral B12H122−
 nido- (from the Latin for "nest") B occupies n vertices of an n+1 deltahedron, e.g., B5H9
an octahedron missing 1 vertex
 arachno- (from the Greek for "spiders web") B occupies n vertices of an n+2 deltahedron
e.g. B4H10 an octahedron missing 2 vertices
 hypho- (from the Greek for "net") B occupies n vertices of an n+3 deltahedron possibly
B8H16 has this structure, an octahedron missing 3 vertices
 conjuncto- 2 or more of the above are fused together
Bonding in boranes
Boranes are electron-deficient and pose a problem for conventional descriptions of covalent
bonding that involves shared electron pairs. BH3 is a trigonal planar molecule (D3h molecular
symmetry). Diborane has a hydrogen-bridged structure, see the diborane article. The description
of the bonding in the larger boranes formulated by William Lipscomb involved:

 3-center 2-electron B-H-B hydrogen bridges

 3-center 2-electron B-B-B bonds
 2-center 2-electron bonds (in B-B, B-H and BH2)

The styx number was introduced to aid in electron counting where s = count of 3-center B-H-B
bonds; t = count of 3-center B-B-B bonds; y = count of 2-center B-B bonds and x = count of BH2
groups.
Lipscomb's methodology has largely been superseded by a molecular orbital approach, although
it still affords insights. The results of this have been summarised in a simple but powerful rule,
PSEPT, often known as Wade's rules, that can be used to predict the cluster type, closo-, nido-,
etc. The power of this rule is its ease of use and general applicability to many different cluster
types other than boranes. There are continuing efforts by theoretical chemists to improve the
treatment of the bonding in boranes — an example is Stone's tensor surface harmonic treatment
of cluster bonding. A recent development is four-center two-electron bond.