Julienne Stephanie Fabie-Agapin

2006-53237

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 Note

1.-CH group is
Carboranes
isoelectronic with BH-
group.
are a class of boron hydride clusters in
which one or more of the BH vertices
2. Two successive
are replaced by CH units.
replacements of BH with
CH will give a neutral
Classes

carborane
CLOSO

NIDO

ARACHNO

(Dalton Trans., 2014, 43, 4924)

The Royal Society of Chemistry, 2014
BORANE to
CARBORANE

Note:

Boranes and Carboranes having the same number of

electrons in their framework will have the similar
structure.
 CLOSO NIDO ARACHNO

-closed -derivative
triangulated -derivative
of closo of nido
polyhedral -removal of
structure -removal of
one vertex one vertex
-all vertices of closo
of of nido
polyhedron. structure.
polyhedron -2n+4e-
are occupied -2n+6e-
-ex. C2B4H8
by B&C C2B3H7
-2n+2e-
-ex.
C2B10H12
C2B4H6
 Preparative Routes
1.Closo Carboranes
Starting compounds: (small and intermediate sized 0-, m-
, and p-carboranes
B2H6, B5H9, and
Formed by:
B10important
Most H14 route to carboranes: a. high energy reactions between
boranes and alkynes
Hydride-Alkyne b. by conversion of nido-carboranes
c. by pyrolysis and electric
Reaction discharge in alkyl boranes
d. by reaction of boranes with
carbon vapours.
May also prepared by:
a. the reaction of alkylboranes with
alkynes
b. hydroboration of alkynyl-boranes
c. 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 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
CnBnHn solids are formed .

Carboranes and general routes of preparation

Bakhshi, et al
 Borane-alkyne reactions in solutions

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 with alkynes in organic solvents.

Carboranes and general routes of preparation

Bakhshi, et al
 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:

The pyrolysis of alkyl boranes at 500-600o C is

particularly useful for the preparation of
monocarbaboranes though the yields are often low, e.g.:

Carboranes and general routes of preparation

Bakhshi, et al
 Cluster expansion reactions

The cluster expansion reactions with diborane

provide an alternative route for the preparation of
intermediate closo-carboboranes, e.g.:

Carboranes and general routes of preparation

Bakhshi, et al
 Cluster expansion reactions

The heating of 1,2-isomer in the gas phase at

470˚C for several hours leads to the formation of 1,7-
isomer. The quantitative yield is obtained by flash
pyrolysis at 600˚C for 30 s .The heating of the 1,7-
isomer for a few seconds at 700˚C results in the
formation of 1,12-isomer with 20% yield.

Carboranes and general routes of preparation

Bakhshi, et al
 2. 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.

Metal acetylides can also be used in lieu of alkynes to

obtain dicarbon or monocarbon carboranes.

Carboranes and general routes of preparation

Bakhshi, et al
Carboranes and general routes of preparation
Bakhshi, et al
 3. Arachnocarboranes

Cluster degradation reactions

1,3-dicarbanonaboranes(13),1,3-C2B7H13 is obtained as
a degradation product when 2,3-C2B9H11 was treated with
chromic acid. The C- 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.:

Carboranes and general routes of preparation

Bakhshi, et al
Carboranes and general routes of preparation
Bakhshi, et al
 WADE MINGO RULES
(Polyhedral Skeleton Electron Pair Theory)

Calculate the Calculate the EP=SE/2

sum of number of
Skeletal pair of
electrons (SE) electrons (EP)
1. Each BH unit
donates 2e- to
skeletal structures. Identify
2. Each CH unit
donates 3e- structure as
3. Valence electron follows:
charge on borane
gives an electron
4. Additional
Hydrogen atom
gives one e- each.
Carboranes and general routes of preparation
Bakhshi, et al
 Application to WADE MINGO
RULES
2-
For B7H7 , Heptahydroheptaborate(2-)
SE=2(B-H) + 3(C-H) + 1 (additional H) + anionic charge on cluster
=2(7)+0+0+2
=16 Note: C, Si, Ge, Sn can be
replaced by BH units;
EP=16/2=8
N, P, As can be replaced by
No. of vertices is 7 BH2 units; and
No. of EP=8; which corresponds to n+1
Thus it is closo borane (no missing vertex) S, Se can be replaced by
BH3 units

Carboranes and general routes of preparation

Bakhshi, et al
END…