BORON CAGE COMPOUNDS

Boranes

Boron hydrides are known as Boranes. These are gaseous substance at ordinary
temperatures. Boranes is the name given to the class of synthetic hydrides of
boron with generic formula BxHy. Borane molecules were often labeled
"electron-deficient" because of their multicenter bonding.

Nomenclature of boranes

i) The latin prefixes mono, di, tri, etc are used before “boranes” to indicate the
number of boron atoms in the compound.

ii) Immediately following the ‘e’ in ‘borane’ the number of hydrogen atoms is
placed in parentheses using Arabic numerals. Examples; B5H11 is pentaborane
(11)

iii) Whereas the names of anions end in ‘ate’ rather ‘ane’. The numbers of both
borane and hydrogens are indicated by latin prefixes. Examples: B10H102- is
decahydrodecarborate (2- )

It is expected that boron would form the hydride BH3, but this compound is
unstable at the room temperature. However, higher hydrides like B 2H6
(diborance). B4H10 (tetraborane), B6H10 (hexaborane), B10H14 (decaborane) etc.
are known. The general formula of boranes are BnHn + 4 and BnHn + 6. In addition
to these, recently discovered series of closed polyhedral structures with the
formula [BnHn]2-. Higher boranes have different shapes, some resemble with
nests, some with butterfly and some with spider's web.

Classification

The structures of boranes can be classified according to the following scheme:

closo boranes have the formula BnHn2- (n vertices of cornered polyhedron are
occupied by boron atoms)
nido boranes are formally derived from BnHn4- ions (1 vertex is missing from
parent closo borane)
arachno boranes are formally derived from BnHn6- ions(2 vertex is missing
from parent closo borane)
hypho boranes are formally derived from BnHn8- ions(3 vertex is missing from
parent closo borane)
klado (or conjuncto) boranes are formally derived from BnHn10- ions(4 vertex
is missing from parent closo borane)

Closo Boranes : These are closed structured (Closo – In Greak, meaning cage)
boranes with the molecular formula [BnHn]2- and skeletal electrons = n+1 pairs
(= 2n+2 electrons). In this structure, there is one boron atom placed at each apex
and there are no B-H-B bonds present in the molecule. All the member of the
series from n=5 to 12 are known. [B5H5]2- is trigonal bipyramidal, [B6H6]2- is
octahedral and [B12H12]2- is icosahedral. All are stable on heating and are quite
inert.

Nido-Boranes: These boranes have nest (Nido – In Latin, meaning Nest) like
structure. Their general formula is BnHn+4 and have (n+2) pairs = 2n+4 skeletal
electrons. On removing one boron atom from an apex of closo structure, nido
structure is obtained. Because, of the lost boron atom, these boranes have extra
hydrogens for completing the valency. The polyhedra in this series have B-H-B
bridge bonds in addition to B-B bonds. They are comparatively less stable than
'Closo', but more than 'Arachno' on heating.

Arachno-Boranes: These boranes have the general formula (BnHn+6) and

skeletal electrons of (n+3) pairs = 2n+6 skeletal electrons. These molecules are
obtained by removing two boron atoms from two apexes of the closo structure
and have spider-web like structure. They have B-H-B bridge-bonds in their
structures and are very reactive and unstable on heating.

Synthesis

The simplest method for synthesis of higher boranes is the controlled pyrolysis
of diborance, B2H6. It is a gas phase reaction. BH3 formed in the first step reacts
with borane to give higher boranes.

8BF3 + 6NaH 6NaBF4 + B2H6

2NaBH4 + I2 B2H6 + 2NaI + H2

Reactions

The important reactions of higher boranes are with Lewis bases, which involve
removal of BH2 or BHn from the cluster or removal of one or more number of
protons:

1. Decomposition by Lewis-bases
Small, hard Lewis bases such as ammonia result in unsymmetric cleavage
ie, the splitting off of the BH2+ moiety.
+ -
B4H10 + 2NH3 [BH2(NH 3)2] + [B3H8]

2. Deprotonation
Strong bases like methyl lithium is required for the deprotonation of
Pentaborane (9).

3. Electrophilic displacement of proton

Electrophilic displacement of proton by the catalytic activity of Lewis
acids like AlCl3 is the basis of alkylation and halogenation of boranes.

Structure and Bonding of cage/cluster compounds

B2H6
In diborane, each boron atom is surrounded by an approximate tetrahedron of
hydrogen atoms. The bridging hydrogen atoms from the boron atom form a
smaller HBH bond angle than that for the terminal hydrogen atoms.
The bonding in diborane is best described by treating each B as sp 3-hybridized.
Two sp3-hybrid orbitals on each boron form the bonds to the terminal hydrogens
( bonds). The remaining sp3-orbitals create the bonds with the bridging
hydrogens (three-center bond).

The approximate combinations of the three orbital wave functions, B1, B2
(approximately SP3 hybrids), and H (an S orbital) result in three molecular
orbitals:

Where b is a bonding MO, a is an antibonding MO, and n is a nonbonding

MO (to be a first approximation). The diagrammatic possibilities of overlap
together with sketches of the resulting MOs and their relative energies are given
below (for one HBH bridge in diborane) :
Each bridging bond (two HBH bonds) thus consists of a bonding MO
containing two electrons and have a configuration b2. This accounts for the
total of 12 bonding electrons and provides the existence of the dimer.

Tetraborane [B4H10]

[B12H12]2- anion

The [B12H12]2- ion is a regular icosahedron of atoms, each of the twenty faces
being an equilateral triangle. All of the hydrogen atoms are external to the boron
icosahedron and are attached by terminal BH bonds. The icosahedron itself
involves a resonance hybrid of several canonical forms. Both two-electron, two-
center B-B and two-electron, three-center BBB bonding are involved.
Examples of other boranes

B5H9

Carboranes

Carborane, any member of a class of organometallic compounds containing

carbon (C), boron (B) and hydrogen (H). They have been combined with
transition metals to yield derivatives called metallacarboranes, some of which
show catalytic activity. Carboranes are electron-delocalized (non-classically
bonded) clusters composed of boron, carbon and hydrogen atoms that may also
contain other metallic and nonmetallic elements in the cluster framework. These
clusters are polyhedra or fragments of polyhedra, and are classified as closo-,
nido-, arachno-, hypho-, etc based on whether they represent a complete
(closo-) polyhedron, or a polyhedron that is missing one (nido-), two (arachno-
)three (hypho-), or more vertices. Carboranes are a notable example of
heteroboranes.

The utility of carboranes as pharmacophores in drug design (molecules that

facilitate recognition and binding by biological macromolecules) motivates
medicinal applications. Unlike boranes, which are generally quite moisture
sensitive, some carboranes are kinetically stable to hydrolysis, permitting their
use in vivo.
Examples and formulas of boranes and carboranes

*this formula of carborane is applicable only for carborane with 2 carbon atoms.

Nomenclature

Rules for naming carboranes are as follows:

i) First of all, give the positions and number of carbon atoms, then the
type of carborane (either closo or nido) and finally the name of the
borane from which the carborane is formally derived and the number
of hydrogen atoms shown in bracket. For example CB5H9 is name as
monocarbonido hexaborane (9). Similarly, the three isomers of
C2B10H12 are named as 1, 2; 1, 7 and 1, 12 dicarbo-closo-
dodecaborane (12).
 ii) Number of atoms in these structure are counted by starting the
numbering from that in the apical position and proceeding through
successive rings in a clockwise direction.
This rule is important in naming the isomers.

Closo-Carboranes or Closed Cage Carboranes

These closo-carboranes (n=3 to 10) have the formula C2BnHn+2 (only for closo
carboranes with 2 carbon atoms), in which the constituents are only terminal.
These are isoelectronic with the corresponding [BnHn]2- ions and have the same
closed polyhedral structures, with one hydrogen atom bonded to each carbon
and boron. No bridging hydrogen atoms are present in the C 2Bn skeleton.
General formula of closo-boranes are CxBn-xHn-x+2 and bonded by n+1 skeletal
pair of electrons. They are considered in three groups.

(a) small, n = 3 - 5 (b) large, n = 6-10 (c) dicarbo-closo-dodecaborane

Preparation

(a) Small closo carboranes (C2BnHn+2 where n = 3 to 5)

(b) Large closo carboranes (C2BnHn+2 where n = 6 to 9)

(c) Dicarbo-closo-dodecaborane
There are three isomers for this carborane. The orthocarborane (1,2
isomer) is the only isomer which can be synthesized directly.
It is synthesized by the base catalysed reaction of acetylene with
decaborane.
 B10H14 + C2H2 C2B10H12 +2H2

Nido-Carboranes or Open Cage Carboranes

These structures are derived formally from one or other of several boranes and
contain from one to four carbon atoms in the skeleton.

General formula of nido-boranes are CxBn-xHn-x+4 and bonded by n+2 skeletal

pair of electrons.

Examples: CB5H9, C2B4H8, C3B3H7, C4B2H6

The large nido carboranes ( n = 4 or 9) are prepared by the base degradation of

ortho-carborane.

Arachno-Carboranes

General formula of arachno boranes are CxBn-xHn-x+6 and bonded by n+3 skeletal
pair of electrons.
Example: C2B7H13
Properties

1, 2 dicarbo closo-dodecarborane-12 is stable in both air and heat. On heating in

inert atmosphere at 450-500 °C, it is converted into 1, 7 isomer i.e. meta or neo
isomer; while at 700 °C it is concerted to 1, 12 isomer i.e. para-isomer.
Structure and isomerizations of the three isomers of dicarba-closo-
dodecaborane

Examples of carboranes

1,3-C2B7H13 1,6-C2B8H10 1,7-C2B9H12

Metallacarboranes

Strong bases attack 1,2-dicarba-closo-dodecaborane (12) with the splitting out

of a boron atom:

The resulting anion is the conjugate base of a strong acid which may be
obtained by acidification:

Conversely, treatment of the anion with the very strong base sodium hydride
abstracts a second proton and to form dicarbollide:
Synthesis of metallacarboranes from dicarbollide

Structure and bonding of [C2B9H11]2- anion

The structure of the [C2B9H11]2- anion is shown in Figure. Each of the three
boron atoms and the two carbon atoms on the open face of the cage directs an
orbital (taken as sp3 for convenience) toward the apical position occupied
formerly by the twelfth boron atom. Furthermore, these orbitals contain a total
of six electrons. They thus bear a striking resemblance to the p orbitals in the 
system of cyclopentadienide anion. Noting this resemblance, Hawthorne
suggested that the [C2B9H11]2- anion could be considered isoelectronic with
C5H5- and should therefore be capable of acting as a  ligand in metallocene
compounds.
Structures of some carbollyl metallocene compounds
Dicarbollyl species Mixed carbollyl- Mixed carbollyl-carbonyl
cyclopentadienyl compound
compound

_________________