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Subject Chemistry

Paper No and Title 11. Inorganic Chemistry –III (Metal π-Complexes and Metal
Clusters )
Module No and Title Module22. Carboranes and general routes for their preparation

Module Tag CHE_P11_M22

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3.Caboranes and their general routes of preparation
3.1 Carboranes
3.2 Preparative routes
4. Summary

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation
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1. Learning Outcomes
After studying this module, you will be able to

• Know about carboranes

• Types of carboranes
• Learn about various methods of preparation of carboranes

2. Introduction
The closely related to the polyhedral boranes and borohydrides are the carboranes more formally
the carbaboranes, a large family of clusters that contains boron and carbon atoms.
Thus, carboranes are mixed hydrides of carbon and boron in which both carbon and boron atoms
exist in electron-deficient molecular skeleton. Carboranes are also defined as the electron-
delocalized boron framework containing one or more carbon atoms. These molecules are non-
classical as the skeletal carbon and boron atoms are involved in delocalized bonding each
typically having five or six neighbors.

3. Carboranes and their general routes of preparation

3.1 Carboranes
Carbon has one more electron than boron, so the C-H moiety is isoelectronic with the BH- or BH2
species. An isoelectronic relationship also exists between C and BH or B-.Hence, it is possible to
replace a boron atom in a borane with a carbon atom (with an increase of one unit positive
charge) and retain an isoelectronic system. The polyhedral carboranes may be considered as
formally derived from the BnHn2- ions in which a BH unit has been formally replaced by an
isoelectronic CH unit. Each C-H group is regarded as donating three electrons to the framework
count. Thus, two such replacements lead to neutral molecule of general formula Bn-2C2Hn. All
such carboranes from (n=5-12) are known either as such or for (n=8-10) as C-C dimethyl
derivatives. The isomeric forms of these carboranes are possible in all cases. The range of
composition in carboranes cages extends from boron rich clusters such as C2B10H12 andCB11H12-
to systems having as many as six skeletal carbon atoms but those with high boron content are
dominant.
The borane anions B10H102- and B12H122- have been studied far more thoroughly than the others
because of their stability. The best studied system is C2B10H12 isoelectronic with [B12H12]2-.Other
dicarboranes are derived from the corresponding pentaborane (5) B5H52- [C2B3H5] hexaborane(6)
B6H62- [C2B4H6], heptaborane (7) B7H72- [C2B5H7],octaborane(8) B8H82- [C2B6H8],nonaborane(9)
B9H92- [C2B7H9] and decaborane(10) B10H102-[C2H8H10] dianions,B11H112- [C2B9H11].The
C2B9H112- anions are known by the trivial name of dicarbolide ion (from the Spanish olla-a pot
reflecting the pot like shape of C2B9).
The carboranes conform to the electronic rules similar to those for boranes and are known as
closo, nido and arachno structures which can formally be regarded as derivatives of BnHn+2 (or
the related anions BnHn2- )BnHn+4 and BnHn+6 respectively. The closo-carboranes have the general

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation
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formula 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 the
isoelectronic B- to give CBn-1Hn+1.The 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.The arachno-carboranes are
present less numerous 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-

3.2 Preparative routes

The reactive boron hydrides B2H6 , B5H9 and B10H14 are used as starting materials to synthesize
carboranes which may be handled safely and be suitable for the use as high energy rocket and jet
fuels. The boron hydride-alkyne reaction is the most important route to carboranes. The
alternative preparative methods are used in view of cost, safety and availability of borane starting
materials. The carborane syntheses involve insertion of carbon into polyborane framework as
boranes provide the required electron-delocalized matrix.The preparative chemistry of carboranes
can be discribed as follows:

I. Closo-carboranes: (Small and intermediate sized and o-, m- and p-carboranes)

Small closo-carboranes include CnBnHn+2(n=3,4,5) and CB5H7 and intermediate sized closo-
carboranes are CnBnHn+2 (n= 6,7,8,9).Small closo-carboranes not larger than C2B5H7 in
appreciable yield are formed by (a) high energy reactions between boranes and alkynes (b) by
conversion of nido-carboranes (c) by pyrolysis and electric discharge in alkyl boranes (d) by
reaction of boranes with carbon vapours.
The alkylated derivatives can also be prepared by (a) the reaction of alkylboranes with alkynes(b)
the hydroboration of alkynyl-boranes (c) the dehalogenation of alkylboron halide with alkali
metals.
Borane-alkyne gas phase reactions : The interactions of lower nido-borane hydrides with
acetylene in vapor phase under high energy conditions such as electric discharge or flash
reactions is an inefficient method to obtain characterizable carboranes as complex mixtures of
small closo-carboranes such as C2B3H5 , C2B4H6 and C2B5H7 alongwith their methyl and ethyl
derivatives and nonvolatile amorphous CxByHz solids are formed .

C2H2
nido-B5H9 closo-1,5-C2B3H5 closo-1,6-C2B4H6 closo-2,4-C2B5H7
500-600oC

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation
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Borane-alkyne reactions in solutions : In order to obtain the carboranes in high yield, the
reactions of boranes hydrides with alkynes are undertaken in solvents such as 2,6-
dimethylpyridine and triethylamine. The nido-RR’C2B4H6 derivatives
(R,R’=H,alkyl,alkenyl,phenyl) have been prepared from the reactions of B5H9 with alkynes in 2,6
dimethylpyridine at room temperature. The closo-carboranes of compositions R2C2B10H10 are
synthesized from the reactions of 6,9-L2B10H12 derivatives of decaborane (L= Lewis base)with
alkynes in organic solvents.

6,9-L2B10H12 RC CR' closo-RR'C2B10H10 2L H2 (R= H,alkyl)

Pyrolysis: Pyrolysis of nido- or arachno-carbaboranes or their reaction in a silent electric

discharge leads to closo-species either by loss of H2 or disproportionation:

C2BnHn+4 C2BnHn+2 H2

2C2BnHn+4 C2Bn-1Hn+1 C2Bn+1Hn+3 2H2

The pyrolysis of alkyl boranes at 500-600oC is particularly useful for the preparation of
monocarbaboranes though the yields are often low, e.g.:

1,2-Me2-nido-B5H7 closo-1,5-C2B3H5 closo-1-CB5H7 nido-2-CB5H9

3-Me-nido-2-CB5H8

Cluster expansion reactions The cluster expansion reactions with diborane provide an
alternative route for the preparation of intermediate closo-carboboranes, e.g.:

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation
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closo-1,7-C2B6H8 1/ 2B2H6 closo-1,6-C2B7H9 H2

closo-1,6-C2B7H9 1/ 2B2H6 closo-1,6-C2B8H10 H2

Isomerization:
The three isomeric icosahedral carboranes viz. o-carborane 1,2-C2B10H12 ,m-carborane 1,7-
C2B10H12 p-carborane 1,12- C2B10H12 are unique both in their ease of preparation and their
stability in air.Of these, an extensive chemistry has been developed for 1,2 –isomer in particular.
The direct reaction of ethyne (acetylene) with decaborane in the presence of a Lewis base
preferably Et2S affords the bulk synthesis of closo-1,2-isomer:
nido-B10H14 2SEt 2 B10H12(SEt2)2 H2

B10H12(SEt2)2 C2H2 closo-1,2-C2B10H12 2SEt 2 H2

The heating of 1,2-isomer in the gas phase at 4700C for several hours leads to the formation of
1,7-isomer. The quantitative yield is obtained by flash pyrolysis at 6000C for 30 s .The heating of
the 1,7- isomer for a few seconds at 7000C results in the formation of 1,12-isomer with 20%
yield.

Fig.2 Isomers of closo-C2B10H12

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )
Module22. Carboranes and general routes for their preparation
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The“diamond-square-diamond” mechanism has been proposed for the 1,2↔1,7 isomerization but
the 1,12 isomer cannot be generated by this mechanism .An alternative mechanism giving both
the 1,7 and 1,12 isomers is the successive concerted rotation of the three atoms on a triangular
face. A third possible mechanism involves the concerted basal twisting of two parallel pentagonal
pyramids comprising the icosahedrons. The different proposed mechanisms may be considered to
be active simultaneously.

II. Nido-carboranes
The characterizable gas or liquid products viz. nido-2-3, C2B4H8 , and nido-1,2 C2B3H7 as open
cage carboranes with the formation of minimal amorphous solids are formed from the vapor
phase borane-alkyne reactions under mild conditions.
C2H2
nido-B5H9 nido-2,3-C2B4H8
200oC
Metal acetylides can also be used in lieu of alkynes to obtain dicarbon or monocarbon carboranes.
LiC C CH3 nido-B5H9 C2H5-CB5H7
The large nido-carborane anions such as CB10H13 ,CB10H11 , 1,2 and 1,7-C2B9H12- and -C2B9H11
- 3-

are also known.

III Arachno-carboranes
Cluster degradation reactions A few archano-boranes have been prepared and characterized
of which the first to be prepared was 1,3-dicarbanonaboranes(13),1,3-C2B7H13 which was
obtained as a degradation product when 2,3-C2B9H11 was treated with chromic acid. The C-

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation
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phenyl, C-methyl and C,Cˈ-dimethyl derivatives are also

known and the structure of dimethyl derivative has been established by X-ray analysis.
The cluster degradation reactions lead to more open structures, e.g.:

base hydrol
closo-1,6-C2B8H10 arachno-1,3-C2B7H12- B(OH)3
OH- + 2H2 O

chromic acid oxidation

closo-2,3-C2B9H11 arachno-1,3-C2B7H13 2B(OH)3 5H+
+ 6H2 O - 6e-

5. Summary
Ø The evolution of carboranes chemistry is related to their applications in drug design,
liquid crystal, nanostructure construction, crystal engineering and incorporating the
thermally stable carborane residues (1,7-C2B10H12) in high polymers such as silicones in
order to increase the thermal stability.
Ø The prefixes closo-,nido- and arachno are also used for carboranes similar to those for
boranes being the derivatives of BnHn+2 ,BnHn+4 and BnHn+6 respectively.
Ø The boron hydride-alkyne reaction is the most important reaction for the preparation of
carboranes.
Ø The small nido-carboranes can be prepared by the reactions of boranes with alkynes
under milder conditions than those used to form closo-carboranes.
Ø Closo-carboranes are the most numerous and the most stable of the carboranes.

CHEMISTRY 11.Inorganic Chemistry –III ( Metal π-Complexes and Metal Clusters )

Module22. Carboranes and general routes for their preparation