Magadh University, Bodh-Gaya

Dr. Partha Pratim Das

Assistant Professor
P.G. Department of Chemistry
Magadh University, Bodh-Gaya

E-Content Title: Carboranes

Stream: M. Sc. (2nd Semester)

Email id: mail.to.parthapratimdas@gmail.com

Carboranes: Carboranes are clusters composed of carbon, boron and hydrogen atoms. These
also can be classified like boranes as closo-, nido-, arachno-, hypho- or klado- based on whether
they represent a complete (closo) polyhedron or a polyhedron with missing one (nido-), two
(arachno-) or more vertices. Carboranes are the most common examples of hetero-boranes.
Electronic structure of carboranes has been described by Wade-Mingos rules. Following three
main categories of carboranes are discussed below.

1. Closo-(Closed) Carboranes: Closo-carboranes have the general ormula CaBn-aHn-a+2 and

are bonded by (n+1) skeletal pairs of electrons. The most common members of the class have
a=2, i.e. C2Bn-2Hn and one or both of the C can be replaced by isoelectronic B- giving CBn-1Hn+1.
Closo-Carboranes have closed triangular polyhedral structures, where all the vertices of the
triangular polyhedral geometries are occupied by boron and carbon atoms. [n+1] Electron pairs
(or 4n+2 skeletal electrons) are involved in this multicentre bonding of closo-carborane [n = total
number of B and C atoms]. Examples:

o C2B10H12: Here n = 12. Wade’s rule suggests that, 2 CH units contribute 2×3 = 6
electrons and 10 BH units contribute 10×2 = 20 electrons to its skeletal structure. Hence, there
are in total, 26 electrons or 13 electron pairs [n+1 = 13] in the multi-centered bonding orbitals of
C2B10H12, indicating towards a closo- kind. Three isomers are possible (ortho-, meta- and para-).

Structure and isomerism in C2B10H12 (dicarba-closo-dodecaborane)

o C2B3H5: Here, n = 5. As per Wade’s rule, 2 CH units contribute 2×3 = 6 electrons and 3
BH units contribute 3×2 = 6 electrons to the skeletal structure. Therefore, 6 electron pairs (n+1 =
6) are present in multicentre bonding orbitals of C2B3H5, dictating as closo- type. Three isomers
are also possible here, which are given below.
2. Nido-(Nest-like) Carboranes: Nido-carboranes have the general formula CaBn-aHn-a+4
and are bonded by (n+2) skeletal pairs of electrons. Again C can be replaced by B- or BH to give
compounds all of which are skeletally isostructural with BnHn+4. These have nest-like geometries
and can be assumed as derivatives of closed triangular polyhedral structures, where one vertex is
removed. Most of the vertices in these clusters are occupied by boron atoms, others by carbons.
There are n+2 electron pairs (or 4n+4 skeletal electrons) involved in multicentre bonding in
nido-carboranes, [n = total number of B and C atoms]. Examples:
o C2B9H13: Here n = 11. According to Wade’s rule, 2 CH units contribute 2×3 = 6
electrons and 9 BH units contribute 9×2 = 18 electrons. 2 Additional hydrogen atoms contribute
2×1 = 2 electrons to the skeletal structure. Hence, total 26 electrons or 13 electron pairs (n+2 =
13) are present in the multicentre bonding orbitals of C2B9H13, confirming as nido- type
structure. Structures of some of the possible isomers, could be obtained experimentally are given
below.

o C2B4H8: Here, n = 6. 2 CH units contribute 2×3 = 6 electrons, 4 BH units contribute 4×2

= 8 electrons and additional 2 hydrogen atoms contribute 2×1 = 2 electrons to the skeletal
structure according to Wade’s rule. So, total 16 electrons or 8 electron pairs (n+2 = 8) present in
multicentre bonding orbitals of C2B4H8, entering it into a nido- catagory.
B1 B1

B5 B6 B5 B6

B4 C2 C4 C2

C3 B3

(2, 3) (2, 4)
 3. Arachno-(Web-like) Carboranes: Arachno-carboranes are present less
numerously than the other two classes. These are characterized by general formula CaBn-aHn-a+6
and are bonded by (n+3) skeletal pairs of electrons. These are structurally related to BnHn+6 (i.e. a
=0); for example C2B7H13 is related to B9H15 and B9H14-. They have web-like geometries and can
be assumed as derivatives of closed triangular polyhedral structures, where two vertices are
removed. Most of the sites are occupied by boron atoms, while others by carbon atoms. There
are n+3 electron pairs (or 4n+6 skeletal electrons) involved in the multicentre bonding in
arachno-carboranes [n = total number of B and C atoms]. Examples:
o C2B6H12: Here, n = 8. Wade’s rule suggests that, 2 CH units contribute 2×3 = 6
electrons, 6 BH units contribute 6×2 = 12 electrons and 4 additional hydrogen atoms contribute
4×1 = 4 electrons to the skeletal structure. Therefore, total 22 electrons or 11 electron pairs (n+3
= 11) present in multicentre bonding orbitals of C2B6H12, confirming arachno- kind. Structures
of some of the possible isomers are given below.

o C2B7H13: Here, n = 9. So, according to Wade’s rule, 2 CH units contribute 2×3 =

6 electrons, 7 BH units contribute 7×2 = 14 electrons and 4 additional hydrogens contribute 4×1
= 4 electrons to the skeletal structure. Thus, total 24 electrons or 12 electron pairs (n+3 = 12)
present in multicentre bonding orbitals of C2B7H13, making it into arachno-kind. Structures of
some possible isomers are given below.
Structural Pattern Correlation between Closo-, Nido- and Arachno- Carboranes: Structural
patterns for closo-, nido- and arachno- carboranes with different vertexes and skeletal electron
pairs are of prime importance. Correlations are shown below. H atoms are omitted for clarity.
Few hypho-carboranes (C2Bn−2Hn+6) also exists, where three vertices from the parent deltahedron
are missing. Conjuncto-carboranes types of carboranes are also formed by joining two or more
preceding types.