896 Fundamental Concepts of Inorganic Chemistry

It has been already mentioned that in fullerenes, the 'It-electron system is more or less localised and
this is why the fullerenes can form adducts by using the localised double bonds. C60 can form an adduct
with Os04 in benzene containing 4-t-butylpyridine. It indicates the existence of localised double bonds.
CMej

(;;;«0""
o
II / ©f
0
(C60 uses two adjacent
- ~o/ 1r"~ ~-atoms for bonding).

ry
CMe j

ra
C60 and C70 can form T)2- adducts by using the 1t-electrons of the localised C = C bonds. Thus, the
fullerenes act just like the alkenes.

ib
C60 + fr(CO) Cl(PP~)2 ~ (,,2 - 60)fr(CO)CI(PPh3 )2
(Vaska's compound

yl
C60 + (,,2 - C2H 4 )Pt(PPh3 )2 ~
m (,,2 - 60)Pt(PPh3 )2 + C2H 4

10.12 STRUCTURE AND BONDING IN HIGHER BORANES AND

he
CARBORANES
The structure and bonding of B2H6 have been already discussed in Sec. 9.21 in terms of the electron
lc

deficient 3c-2e (B-H-B) hydrogen bridge bonds.. Here we shall mainly discuss the higher boranes
having the cage-like structures. Alfred Stock, a Gemlan chemist prepared several members of boron
ea

hydrides having different formulas.

Hydrogen poor group represented by B"Hn + 4 (e.g. Bs H9 , BgH 12 , etc.) and hydrogen rich group
th

represented by B"Hn + 6 (e.g. B4H 10' B~Hll etc).

Recently, other series represented by BnH;- (e.g. B 6 Hi-, B10H12o-, B12 H 1;-, etc.) and BnIr;,+7 (e.g.
e/

BsH l-2 ) have been reported.

Most of the boranes are highly reactive towards O2• Among the neutral boranes, only B 1oH14 can be
t.m

handled in air.

10.12.1. Classification and Different Series of Boranes

The boron hydrides are classified in different series:
(a) Closo-serics: These are isoelectronic with B"Hn + 2 or BnH;-. They normally exist as BnH;-.
Examples: BsH;- to B12H122- (Le. n = 5 to 12). .
The closo-borane anions (Greek closo means cage) have closed polyhedral clusters of n-boron
atoms (i.e. n-vertices).
Characteristics :
• Deltahedral structure (deltahedron means a regular polyhedron with triangular faces);
• Cage like structure;
• No BHB (3c-2e) bond;'
• No BH2 group;
 Covalent Compounds: Characteristics, Structure and Reactivity 897

• Isoelectronic with the neutral borane B,/in + 2 which is less stable than B,/in2-.
• (n + 1) skeletal electron pairs (SEPs) for B-framework (cf. Wade's rule).
(b) Nido-series: The~e are isoelectronic with B,/in + 4.
Example: B2H6 , B5H9 , BsH8-, B6H 1o , B8H 12 , B 10H 14 , B 10H I3 -. The structure of these boranes
looks like nest-like (Latin word nido means nest).
Characteristics :
• Nest-like deltahedral structure with a missing vertex;
• Isoelectronic with B,/in + 4;

ry
• (n + 2) skeletal electron pairs (SEPs) for B-framework.
(c) Arachno-series: These are .isoelectronic with B,/in + 6.

ra
Examples: B4H 10 ; BsH11 ; B6H 12 ; B8H 14 ; BgH15' etc.
Arachno (Greek word meaning web-like or spider's web) series possess the web-like structure.

ib
Characteristics :

yl
• Web-like deltahedral structure with two missing vertices.
• (n + 3) skeletal electron pairs for boron framework.
m
(d) Hypho-series: These are isoelectronic with B,/in + 8.
Examples: BsHi;, BsH I21-, no neutral borane in this group.
he
Hyphe (Greek word meaning net-like)
Note: Boranes BpHp+q Le. (BH)pHq can be formulated as (BH)n(BH 3)x where n = 0, 1,2,
..., I{) and x = 1,2,3, ..., e.g. B2H 6 == (BH3)2; B3H 7 == (BH)(BH3)2; B5H 9 == (BH)3(BH3)2;
lc

116 H 12 == (BH)3(BH3)3' etc. In fact, for nido-series, x = 2 (and q = 4) and for arachno-series, .
x = 3 (and q = 6).
ea

In general, the thermal stability order is :

cwso-)nido-)~achno-)~ho-
th

Conjuncto-boranes (B"Hm) : These are formed by joining the subunits of two or more of the
different series. The examples of conjuncto-boranes (Latin conjuncto means join together) are:
e/

B8H 18 , B 1oH16' B 15 H23 , B 16H20 , etc.

t.m

The different series are related as follows

-BH 2+ -BH 2+
BnH;- ) BpH p + 4 ) BmHm+ 6
+4H+ +2H+
(closo -) (p=:=n-I) (m = n - 2)
(nido -) (arachno -)
-2BH2+
+6H+
f
-BH 2+, +4H+ -BH 2+,+2H+
B6 H 62- ) BsH 9 ) B4 H 10
(closo-) (nido-) (arachno-)
-BH+, +4H+ -BH 2+, +2H+
B7 Hi- · ) B6 H10 ) Bs H l1
(closo-) (nido-) (arachno-)
898 Fundamental Concepts of Inorganic Chemistry

CLOSO-series (BnH~- )

ry
(8H)SH 4 == 8 SHg (BH)4 HS == B4 H 10
=
8 1 - 82 8 1 - 83 =
8 1 - 8 2 185 pm;

ra
= 8 1 - 8 4 =8 1 - 8 s 81 - 83 =172 pm.
= 169 pm,
8 2 - 8 3 , etc. =180 pm.

ib
yl
m
he
(8H)sH S == 8 5 H 11
= =
8 1 - 8 2 8 1 - 8 5 187 pm
= =
8 1 - 8 3 8 1 - 8 4 172 pm.
lc

=
8 2 - B3 8 4 - 8 5 = 176 pm.
(8H)sH 4 == 8 sH 10 .=
8 3 - 8 4 177 pm.
ea

8 1 - 8 2 =170 pm, 8 1 - 8 4 ~'

=
=180 pm, 8 2 - 8 3 179 pm,
8 3 - 8 4 = 174 pm,
th

8 4 - 8 5 =160 pm.,
e/
t.m

(8H)10 H4 == 8 10H 14
=
8 1 - 8 3 171 pm, 8 2 - 8 s
= 8 4 - 8g = 172 pm, 8 1 ~ 8 2 .4.7,8
=B2 - 8 5,7 = 8 6 - 8 5•7
2- 2- = 8 4 - 8 8,10 = Bg - 8 8,10
(8H)g == 8gHg =177 pm.
Fig. 10.12.1.1. Framework of some representative boron hydrides (0 for B • for H)
 Covalent Compounds: Characteristics, Structure and Reactivity 899

10.12.2 Nomenclature of Boranes

(a) Neutral boron hydrides are named as boranes. The Greek prefix (e.g. di, tri. tetra,penta, hexa,
hepta, octa, ennea, deca, etc.) indicates the number of B-atoms. For neutral species, an Arabic
number in the parentheses gives the number of H-atoms.
Examples: B 1H 6 : diborane (6) [commonly called diborane as there is no alternative possibility];
B sH 9 : pentaborane (9); B 6H IO : hexaborane (10); B'//14 : octaborane (14); B ull14 : decaborane
(14); Bc/lls : enneaborane (15); B I4H 20 : tetradecaborane (20) etc.
(b) The anionic species are named as hydroborates and the Greek prefix indicates separate~y the

ry
number of hydrogens and borons. The charge of the anions is given within the parenthesis.
Example: B sH8: octahydropentaborate (1-); BloH;;: decahydrodecaborate (2-); BI1H;;:

ra
dodecahydrododecaborate (2-).
Note: Sometimes, the structural typ_~ is also specified.

ib
Examples: BsH8 : octahydro-nido-pentaborate (1-); BI1H~- : dodecahydro-closo-dodecaborate
(2-); ~OH14: nido-decaborane, etc.

yl
10.12.3 Structure and Molecular Framework of Hydrides of Boron
m
With the exception of B2H6 and B3 H;, boranes' cage structures are formed based on polyhedra or
polyhedral fragments having equilateral triangular faces with the BH groups at the vertices. Such
he
polyhedra are commonly called deltahedra. The triangular faces of the polyhedra look like the upper-
case Greek delta (~). This is why, such polyhedra are called deltahedra. The deltahedra from n = 4 to
lc

n = 12 (where n gives the number of vertices) are: tetrahedron (n = 4), trigonal bipyramid (n = 5),
octahedron (n = 6), pentagonal bipyramid (n = 7), dodecahedron (n = 8), tricapped trigonal prism (n
ea

= 9), bicapped square antiprism (n = 10), octadecahedron (n = 11), and icosahedron (n = 12). In this
list of polyhedra, the example of cube is excluded.
th

The deltahedral geometry is common for different cluster structures like boranes, carboranes,
Zintl ions etc.
e/

For a deltahedron with n-vertices for the Mn cluster, there are n + 1 bonding MOs. Always the
clusters may not adopt the geometries of closed deltahedra. If no vertex is missing, then it gives the
t.m

closo-geometry, if one vertex is missing, it gives the nido-geometry, if two vertices are missing, it
gives the arachno-geometry. This is illustrated for boranes and carboranes.
If all the vertices of a deltahedron are occupied as in closo-series (BnH;-, n = 6 to 12), the structure
becomes closo type. The dicarboranes Bn _ 2C2Hn (n = 5 to 12) also belong to this group.
Nido-series : If one BH unit from a closo-structure is removed but the electron pair is retained by
the residual structure, then the resultant structure becomes nido-type which looks cup-like or nest-
like. Thus, in a nido-structure, one vertex remains missing compared to the parent closo-structure. On
reduction of a closo-molecule, a nido-molecule may be obtained.
closo - B9 C2 H)) + 2e ~ nido - B9 C2 H)2)-
Some common examples of nido-boranes are: B2H6 (a triangle lacking in one B-atom), BsH9 (an
octahedron lacking in one B-atom), B6H 10 (a pentagonal bipyramid lacking in one B-atom).
Arachno-series: If two vertex B-atoms (= 2BH2+ units) are removed from a closo-structure, then it
leads to a arachno (web-Iike)-structure. Thus, an arachno structure is more open than the corresponding
900 Fundamental Concepts of Inorganic Chemistry

Trigonal
Tetrahedron (4) bipyramid (5) Octahedron (6) Pentagonal
(Td ) (D 3h > (Oh) bipyramid (7)

ry
(D Sd )

ra
ib
yl
Capped Dodecahedron (8) Tricapped trigonal
octahedron (7) prism (9) (C3v )
(D 2h )
m
he
lc
ea

Bicapped square Octadecahedron (11)

antiprism (10) Icosahedron (12)
th

(D4d ) (/ >
h
Fig. 10.12.3.1. Structures of deltahedra (Le. regular polyhedra with triangular faces) for boron hydrides
e/

and' carboranes. B or G-atoms are placed at the vertices.

Note : The lines joining the vertices do not represent the bonds.
t.m

nido-structure which is again rnore open than the parent closo structure. In the arachno structure, the
resemblance to the parent closo-structure is less apparent. The gradual transition from closo- to arachno-
structure is illustrated in the following example:

-BH 2+, +4H+ -BH 2+, +2H+

B6 HJ- ) BsH 9 ) B4 H 10
(closo-) (nido-) (arachno-)
(octahedral) (square pyramid (butterfly like structure
== octahedral minus == octahedron minus
one vertex) two cis-vertices)
It is important to note that each of the above three species possesses 7 framework or skeletal
electron 6airs. In fact, the number of skeletal pairs (8) available for framework bonding determines
the nature of structure (cf. Wade's rule, to be discussed later on).
 Covalent Compounds: Characteristics, Structure and Reactivity 901

A similar situation is illustrated below:

2 -BH2+ +4H+ -BH2+, +2H+

closo - B7 H 7 - , ) nido - B6 H 10 ) ~rachno - BsH ll
There is a good correlation for the structures of closo-, nido- and arachno boranes. It is illustrated
in Fig. 10.12.3.2 and 3 (cf. R.W. Rudolph et al., Inorg. Chern., 11, 1974, 1972; R.W. Rudolph, Ace.
Chern. Res., 9, 446, 1976).

ry
ra
ib
yl
m
he
lc
ea

Nido-B aH10
th
e/
t.m

Fig. 10.12.3.2. Generation of arachno-BsH11 (a) and arachno-B4 H10 (b) from their precursor closer
structures through the successive removal of BI-P+ groups. (0 for B, • for H).
902 Fundamental Concepts of Inorganic Chemistry

Nid~Bn-1Ht1

ry
ra
ib
yl
m
he
lc
ea
th
e/
t.m

Fig. 10.12.3.3. Generation of nido- and arachno-boranes from their precursors through the successive
removal of BH 2+ groups. (0 for B, • for H).
 Covalent Compounds: Characteristics, Structure and Reactivity 903

Regular polyhedron Removal of Removal of

Closo-structure - - - - - - + ) Nido-sttucture - - - - - 4 ) Arachno-structure
(n-vertices) one BH2+ (n - 1 vertices) of one BH2+ (n - 2 vertices)
group group
e.g. Octahedron (Oh) ----~) Square pyramid ------..) Butterfly
(n = 6) (n = 5) (n = 4)
(Oh - 2 cis
vertices)

ry
Note:. The regular polyhedra with triangular faces are also described as deltahedra.
• In attaining the nido-structure from its precursor closo-structure, the most highly connected
vertex of the closo-framework is to be removed. This is illustrated in Figs. 10.12.3.2 and 3.

ra
Table 10.12.3.1. Characteristics of some common closo-, nido- and arachno-boranes

ib
(cf. PSEPT I.e. Wade's rule)
Type Skeleton electron Geometry

yl
pair (SEP)
n+l n = 5 (Trigonal pipyramid, TBP)
m
= 6 (Octahedron, 0h)
= 7 (Pentagonal bipyramid, PBP)
he
= 12 (Icosahedron)

n+2 n = 4 (Tetrahedron, Td == TBP - one axial vertex)

lc

= 5 (Square pyramid == 0h - one axial vertex)

= 6 (Pentagonal pyramid == PBP-one axial vertex)

ea

Arachno- n+3 n = 3 (Triangular == TBP - both axial vertices)

(Bn H n + 6 ) = 4 (Butterfly == 0h - 2 cis-vertices)
th

= 5 (PBP - 2 vertices)

H:
Structure of boranes in terms ofstructure of B12 2 : The structure of symmetrical borohydride
e/

ion, B12H122- is very much important in understanding the structure of higher boranes. It gives a regular
t.m

icosahedron (called B I2-icosahedron) with 20-equilateral triangular faces (cf. Fig. 10.12.3.4). All the
H-atoms are present in B-H terminal 2c-2e bonds. Both B-B (2c-2e) and B-B-B (3c-2e) bonds are.
involved in developing the structure. Starting from the Bl 2-icosahedron unit, B 1c1l14 can be obtained by
removing the B1 and B6 atoms from the B l2H l2-framework and the extra/our H-atoms are involved to
produce the B-H-B bridges (3c-2e bonds).
B6H 10 (pentagonal pyramid) possesses the skeleton equivalent to the apical fragment of the.
icosahedron skeleton of BI2HI22-' Similarly, structures of many other boranes can be derived from the
skeleton of BI2H122-'

10.12.4 Skeletal Electron Pair Counting and Wade's Rules: Polyhedral Skeletal Electron
Pair Theory (PSEPT) (cf. Sees. 10.12.7, 12.8.5-6)
The structure ofboranes can be predicted from their formula. Wade's rule can calculate the number of
electrons for framework ofthe deltahedron. These framework electrons are called skeletal electrons. It
is assumed that the building block of the deltahedron are the B-H units (2c-2e bond). Each B-atom
904 Fundamental Concepts of Inorganic Chemistry

Removal of.
8 1 and 8 s

ry
(BH)f2" ==B 12 H f2"
(Icosahedron)

ra
ib
yl
Removal of
8 7 to 8 12 m
he
(BH)sH 4 == BsH 10
Fig. 10.12.3.4. Development of the skeleton of 8 10 H14 and 8 s H10 from the icosahedron skeleton of
lc

8 12 H:2-·
ea

uses one sp-hybrid orbital and one valency electron for the B-H linkage. If a B-centre forms more than
one B-H terminal bonds then except the one other bonding pairs will be considered for skeletal bonding.
th

It indicat~s that each B-atom can provide 3 orbitals (1 sp + 2 pure p-orbitals) and 2 electrons for
framework bonding. The sp orbital of B available for skeletal bonding is called radial orbital pointing
e/

towards the interior of the fragment. The remaining two p-orbitals of B available for skeletal bonding
are called tangential orbitals which are perpendicular to the radial orbital. For a closo-borane B"Hn + 2
t.m

Le. (BH)"H2' the number of skeletal electrons is 2n + 2 (= n + 1 pairs) where each BH unit provides 2
electrons and 2H-atoms provide 2 electrons. Similarly, a nido-borane B"Hn +4 Le. (BH)"H4 can provide
2n + 4 electrons (i.e. n + 2 pairs) for framework bonding. In fact, depending on the number ofskelE!tal-
electron pairs (SEP simply denoted by S), the different series can be classified.
B"Hn + 2 (closo-series) : n + 1 skeletal pairs; B"Hn + 4 (nido-series) : n + 2 skeletal pairs; B"Hn + 6
(arachno-series) : n + 3 skeletal pairs; B"Hn + 8 (hypho-series) : n + 4 skeletal pairs.
For (BH)llq +clC+ (see Sec. 10.12.6, 9), S = p + 1 (closo-series), = p ~ 2 (nido-series), = p + 3
(arachno-series), = p + 4 (hypho-series). However, it may be convenient to c~i1culate the value of S by
considering the neutral boron hydride.
For calculation of S and identification of carboboranes, it has been discussed in Sec. 10.12.9.
Wade's Rule, PSPT : Carbonyl Clusters and Zintle Cluster Ions
These aspects have been discussed in Sees. 12.8.5 and 12.8.6.
 Covalent Compounds: Characteristics. Structure and Reactivity 905

10.12.5 Calculation of the Number of Electron Deficient Bonds

By calculating the total number of available valence electrons and valence orbitals, the number of
electron deficient bonds (Le. 3c-2e bonds) can be calculated. This aspect is illustrated in the following
examples.

Table 10.12.5.1. Calculation of the number of electron deficient bonds in boron hydrides
Species No. ofvalence No. ofvalence Deficiency ofelectrons No. of3c-2e
orbitals electrons to fill in the bonding MOs bonds

ry
2 x 4 + 6 x 1 = 14 2 x 3 + 6 x 1 = 12 14-12=2 2
4 x 4 + lOx 1 = 26 4 x 3 + lOx 1 = 22 26 - 22 = 4 4

ra
5 x 4 + 9 x 1 = 29 5 x 3 + 9 x 1 = 24 29 - 24 = 5 5

ib
These electron deficient 3c-2e bonds may be of different types (cf. Fig. 10.12.5.1).

Involved orbitals MD-dlagram

yl
H Representation
H
m r'\
8 ,8
H
he
or
H or M
A 8 B
B B
lc
ea

(a) 3c - 2e 8 - H - 8 bridge bonds

th

,
,~
,
8 ,' ,,
8
~ " ~ ~
e/

p " , or
B B B B
",,~,"
,
, " B
t.m

~--
" " s-p hybrids
\---*-,'
(b) 3c - 2e open B - B - B bridge bond

,,J
8 "
---~-----
SP3_~Ybrid~ ""'-f-

(c) 3c - 2e closed B - B - B bond

Fig. 10.12.5.1. Representation of 3~2e bonds involved in the structure of boranes (cf. Sec. 9.21 fo~
details).
906 Fundamental Concepts \I. Inorganic Chemistry

~
H

• 3e:-2e hydrogen bridge bo~d :

or
B B
or n
B B

B
• 3o-2e open boron bridge bond :
~
~ ~
or
B
~B

~S

ry
• 3o-2e close boron bridge bond :

ra
• 2o-2e boron-boron bond : B-B

ib
• 2o-2e terminal boron-hydrogen bond: B-H or BH
Fig. 10.12.5.2. Five bonding constituents and their topological representations used in the structures

yl
of boranes.
Note : 5 gives the no. of 3o-2e BHB bonds; t gives the sum of 3o-2e BBB bonds (both open and
m
close);·y gives the no. of 2o-2e B-S-bonds; x gives the no. of additional 2o-2e B-H bonds, Le. no.
of BH2 groups (if no BH3 group).
he
H
H H I H
lc

H,f\/H H,rSI)/H
B B
B B
H/"-../'H H/( )'H
ea

H H'--f~
(B 2H6) H
th

styx =2002 (84 Hg)

styx = 4012
e/

H
I
t.m

H(S~H.
H-s,",",,--I:-s- H
H,A/H
ByB) l JJJ
H ( Iti\ H I iyS,
B 1\ B
H/I HH I'H
H-Bfl.B~B-H
H H
(Canonical structures of 8 sH11 )
~~~
I
=
(styx 3203) H
A representative canonical
structure of 8 10H14
(styx = 4620)
Fig. 10.12.5.3. Representation of bonding in some representative boranes in terms of Lipscomb's
semitopological (styx) scheme.
 Covalent Compounds: Characteristics, Structure and Reactivity 907

The B-H-B bonds are numbered as sand B-B-B (both open and close type) bonds are numbered
as t. By using the 5 bonding units (cf. Fig. 10.12.5.2) Le. 2c-2e B-H terminal bond, 3c-2e B-H-B
hydrogen bridge bond, 2c-2e B-B bond, 3c-2e open boron bridge bond, and 3CL-2e close boron bond,
Lipscomb developed the semitopological descriptions of the structure and bonding of the boranes
(Fig. 10.12.5.3). .
10.12.6 stxy Numbers and Topology of Boron ~ydrldes

In all boron hydrides and carboranes, each B-centre is at least bonded with one H-atom through a 2c-

ry
2e a-bond and it gives a terminal B-H bond. In addition to this, there may be B-H-B (3c-2e) bonds
(numbered by s), 3c-2e B-B-B (both open and close types) bonds (numbered by t), 2c-2e B-B bonds
(numbered by y) and additional 2c-2e B-H (numbered by x). Thus, x denotes the number· of BH2 group

ra
(ifno BH3 group). By calculating the values of s, t, y and x, Lipscom and coworkers developed a system
to describe the topology of the boron hydrides. The values of s, t, y and x can be calculated by using the

ib
equations of balance.

yl
Case-I: Neutral borane SpHp + II' I.e. (SH)pHq
(a) Hydrogen balance equat/on: I q =s + x I
m
The q H-atoms are distributed in B-H:B (s) and additional B-Hterminal bonds (x).
he
(b) Three centre orb/tal balance equation: Ip=s +t I
In (BH)/lq' the number of electron deficient bonds is p (cf. Table 10.12.5.1), Le. per B-atom, one
lc

3c-2e bond is produced. Thus the sum of the number of B-B-B bonds (both types t) and B-H-B
bonds (s) equals to the number of B-atoms.
ea

OO~~~~~~~~:I-p-+-~-q-=-s-+-t-+-y-+-x-o-r-p-=-t-+-y-+-_--o-r-y-=---~-~---X~)I
th

Each B-centre provides three electrons and each H-atom provides one electron. Thus the total number
of bonding electrons = 3p + (p + q) x 1, Le. (2p + q/2) electron pairs. The total number of bonds = (p +
e/

x) + + t + y = number of bonding pairs Le. 2p + 1 = p + s + t + y + x; or, p + 1 = s + t + y + x.

S
t.m

2 2
Here, (p + x) gives the total number of terminal 2c-2e B-H bonds.
Using the hydrogen balance equation, q = s + x, and three centre orbital balance equation,
p = s + t, we can write:
p =t + y +1; or s + t =t + Y +
2
(x s);
+
2
or, y =.!. (s - x)
2
By using the equations of balance, the topology . o f the neutral boron hydride (BH)/lq Le. B/lp + q
can be expressed by styx numbers. In solving the equations, thefo//owing conditions or restrictions
must be satisfied: .
I-i-~-s-~-q-an-d-S-'t-,-y-a-n-d-x-~-o I
Clarification ofthe restrictions: The number (s) of BHB bridges lies in the range of q to q/2. The
additional q Hs atoms are distributed in s number of BHB bonds and x number of additional BH
terminal bonds, Le. q = s + x, and consequently s ~ q.
908 Fundamental Concepts of Inorganic Chemistry

We have: p = 1 + Y + q/2; or (s + I) = 1 + Y + q/2; or s = y + q/2; Le. s ~ q/2.

It is evident that there are four variables (s, I, y and x) but only three independent equations are
available. By using the above restrictions the allowed solution is to be taken into consideration.
Examples:
B1,H6 , i.e. (BH)1,H4 : It leads to p = 2 and q = 4. The involved equations are:
q = 4 = s + x; p = 2 = s + I; P + q/2 = (s + x) + I + Y
or 2 + 2 = 4 + 1 +Y
1+ Y = o.

ry
Le.
The solutions are:

ra
s y x q

ib
2 o o 2 4 } Acceptable, s, t, y, x ~ 0, q/2 ~ s ~ q
3 -1 1 1 4
} Not acceptable as t < 0

yl
4 -2 2 o 4
m
The acceptable styx number is 2002. It indicates that there are two 3c-2e B-H-B bridges (s), no
3c-2e B-B-B bond (I), no 2c-2e B-B bond (y) and two addilional 2c-2e B-H terminal bonds (x). Thus
he
the structure:
H H H
" /
"B/ (styx = 2002)
lc

/8, / '
H IY H
ea

B sH 9 : Now let us consider the case of BSHg Le. (BH) sH4 (nido-species). It leads to p = 5, q = 4'and
the required balance equations are:
q = 4 = s + x; p = 5 = s + I; P + q/2 = (s + x) + 1 + Y
th

Le. 5 + 2 = 4 + 1 + y, or t + y = 3
e/

The solutions are:

s y x q
t.m

2 3 o 2 4 ] All are acceptable. Thus an unequivocal structure is not predicted. This

3 2 1 1 4 is the limitation. However, the structure with the highest symmetry is
4 1 2 o 4, always pre/erred. The 4120 structure explains the properties ofthis borane.
H
.~~/H
Structure of B 58 9 (4120) is: HC>-~H
~~
H
All the possible structures of BSHg are shown in Fig. 10.12.6.1 a.
Some topological representations in terms of styx number of neutral boron hydrides are given in
Figs. 10.12.5.3 and 10.12.6.1.
 Covalent Compounds: Characteristics, Structure and Reactivity 909

H, /H
B-H-B)
H( >-B~ H
B B 1
H/ '-!!.-/ 'H
H
styx =3211

(a) Semitopological representation of BSH g ; The most

=

ry
preferred structure is given by styx 4120

ra
H
I
H HrB,H H

ib
H>'tIJ<H
HBH
I

yl
H
styx = 4012 styx = 3103
(b) Semitopological representation of B 4 H10
m
(Most preferred structure is:
styx = 4012)
he
H
I
tl
H H
lc

y!",\ H H

H-B~B-H HH(\~t~)HH H-B~~~B)H

ea

H'B~B
th

B---H-B B R_B
/ '-----/ "H HI \H I I
e/

H H H H
styx = 3311 styx = 4220 styx = 2402
t.m

(d) Structures for 8 6 H10 ; most stable for styx =4220

H H H H
\/ I I
H(B H
H-BA B/
H\r
B
~/H
B H
H~(BJ:HB}~
(~I B/ \ \
H' / ,H H H( 7 "' H-B- --< >-- -B-H
/B yB - H- B.J...B.J...B- H \ \ I B I~ )
H B)H ~~~ H~B!L-l-B~H
/\ I I I
HH H H H
styx =4212 styx =4212 styx = 4620
(e) Two canonical forms of B eH12 (f) 8 10H 14

. Fig. 10.12.6.1. Semitopological representation of some boranes in terms of styx number.

910 Fundamental Concepts of Inorganic Chemistry

B 4H 10 : This is (BH)4H6 (Le. a member of arachno-series). The required balance euations 'te given
below: .
p = 4; q = 6; s + t = p = 4; and s +. x = q = 6
It leads to :

s + t + y + x = p + "2 7 ·I.e. y + x = "2

q = 4+3= q =3

The solutions are:

s y x q

ry
3
4
1
o
o
1
3
2
6
6
} All are acceptable (~:!> s :!> q)

ra
The structures for styx = 3103 and 4012 are shown in Fig. 10.12.6.1 b.

ib
BsH11 i.e. (BH)sH, : It is a member of arachno-series.
q
= 5; q = 6; s + x = q = 6; s + t = p = 5; y + x = "2 = 3

yl
p

..
Restrlctlons : "2
q ~
· 3 ~ s ~ 6·
s ~ q I.e.
m
s y x q
he
3 203 6 ]
4 1 1 2 6 All are acceptable solutions (Structures are shown in Fig. 10.12.6.1 c)
lc

50216

t=
ea

B 6H 10 i.e. (BH)6H 4 : p = 6; q = 4; s + t = p = 6; s + x = q = 4; Y + x = 2.

t
th

Condition: .5 s .5 q, i.e. 2 .5 s .5 4
e/

s y x q

2 4 o 2
t.m

3 3 1 1 : ] All are acceptable solutions (Structures are shown in Fig. 10.12.6.1 d)

4 2 2 o
Case-II: Charged species [(BfflpHq+ JOt-
Here the relevant equations are:

s + x = q + c; s + t = p + c; y = "21 (s - x - 3c); and p = t + y + c + ql2

The relation, p = t + y + C + q/2 can be attained as follows :

In [(BH)pHq+c]c+, theframework electron counting is obtained in the following way.
1 1
1 electron pair from each BHunit; 2" electron pair from each of the extra H-atoms, Le. (q + c); - 2"
electron pair from each + charge, Le.
 Covalent Compounds: Characteristics, Structure and Reactivity 911

No of skeletal pairs(S) = p+k(q + c) -k c = p +f =s +t + y+ x =q +c+ t+ Y

S = s + t + Y + x (cf. definition for S, Secs. 10.12.4, 10.12.6).

or, Ip =t + Y + c + f I and Iy =k(s - x - 3d I

Total electron count (TEe) = S + no. of electron pairs involved in forming the (BH) units =
(S + p) pairs. r

ry
Thus the total number of bonds = p + S + t + Y + x.
Note: The series is determined by the value of S.

ra
s = p +f = P + I (closo-series), p + 2 (nido-series), p + 3 (arachno-series), p + 4 (hypho-series).

ib
B2Hi: For B 2H 7-, i.e. (BH)2HS-: p = 2, q + C = 5, C = -1, i.e. q = 6. Restrictions: t, x, y ~ 0;

f = 3, i.e.
yl
2c + ql2 $ s $ q + c, i.e. 1 $ s $ 5. It leads to: s
m = 1, t = 0, Y = 0, x = 4, arachno type.

The relevant structure is:

H"", /H l-
he
H - B-H - B - H (i.e. styx = 1004)

H / "'" .H
lc

B#18-: For B3H g-, i.e. (BH)3H5~: p = 3, q + c =5, c =-1, i.e. q = 6, f =3, i.e. arachno type. The
ea

allowed solutions are: styx = 1104 and 2013. Thus, the structures are:

l-
th

H""'I/H
e/

H"", A /H
t.m

H/BY"H
H
(styx: 1104)

Note: Resonating structure: The topological structure of pentaborane (9), i.e. BsHg has been shown
in Fig. 10.12.6.1 a. From the structural studies, all the 4 basal B-atoms are equivalent with respect to
the apical B-atom. In fact, all the Bapical - Bbasal distances are equal (= 169 pm), and all the 4 edge
lengths in the basal plane are equal (= 180 pm). To interpret these observations, 4 equivalent canonical
structures of the skeleton for 4120 topology (cf. Fig. 10.12.6.1a) of BsHg are proposed.

B B ByB B"" /B
~B
>-B( • B ~---..
.. i B

B
"B
/ ~
B
B B
B
/'"B B
A B
912 Fundamental Concepts of Inorganic Chemistry

Because of this delocalisation, its stability is enhanced. The above resonating structures are drawn
by involving the localised 3c-2e boron-boron-boron bonds and 2c-2e boron-boron bonds. However,
the observation can be also explained by considering the formation of seven 5-centred delocalised
MOs in which the lowest three MOs are occupied by three electron pairs. In constructing the B s-
framework, the basal 4 B-atoms provide 4 AOs and the apical B-atom provide 3 orbitals (one sp + two
p). Other resonating structures for B sH9 (styx = 4120) having the open BBB bond instead of the ~losed
BBB bond are also possible.
H H

ry
((D~ (BWB)

ra
H /a'".. )H --. H ~~ H
~ "-.Y

ib
H H
Here the above resonating structures are drawn by involving 3c-2e open BBB bond and 2c-2e B-B

yl
bonds.
In B sH 11 , out of26 electrons, there are 2 pairs for the formation of3c-2e BBB bonds. These 2 pair
m
electrons may be involved in two ways: two closed 3c-2e BBB bonds or (one closed + one open)
3c-2e bonds. The possible resonating structures are shown in Fig. 10.12.5.3 for the 'styx' no. 3203.
he
It may be pointed out that for B1(1I14' there are 24 canonical forms.
Limitations ofstyx number method: The styx number method is convenient to represent the structure
lc

and bonding ofboranes. However, there are some limitations:

(i) It does not always yield a unique set of styx number. Consequently, different structures are
ea

predicated. The most preferred structure is then selected by considering other criteria.
(ii) Even for a particular styx number, different structures can be drawn by varying the number of
th

3c-2e open and closed BBB bonds keeping their sum (t) constant.
For example, B sH 11 (styx = 3202) can be drawn in two ways: 1 open BBB bond + 1 closed BBB
e/

bond or 2 closed BBB bonds. These two canonical forms are shown in Fig. 10.12.5.3.
Structure of B sH 9 (styx = 4120) can -be -drawn in two ways: 1 open or closed BBB bond. The
t.m

structure containing the closed BBB bond is shown in Fig. 10.12.5.3. The possible resonating
structures for this form have been discussed already. .

10.12.7 Molecular Orbital Picture of Higher Boranes (cf. Sec. 10.12.4)

A terminal B-H 2c-2e bond is constituted by using one electron and one orbital of the B-atom. It
leaves three orbitals and two electron per B-atom for skeletal bonding. To produce the segment
BH, the boron centre uses one of its sp-hybrid orbital and another sp hybrid is kept for skeletal bonding
pointing towards the interior of the fragment. This is called radial orbital. The remaining two
p-orbitals (for skeletal bonding) are called tangential orbitals which are perpendicular to the
radial orbital. Thus each boron can provide 3 orbitals (1 radial orbital + 2 tangential orbitals) and 2
electrons for skeletal bonding.
In closo- B6Hi-, there are 18 Mas for skeleton. There are 7 skeletal pairs (cf. Sec. 10.12.4) and
these are housed in the lowest 7 Mas (one a lg + three t lu + three t2g ). There is a large energy gap
between the HOMO (Le. t2g set) and LUMO (Le. t2u set).
 Covalent Compounds: Characteristics, Structure and Reactivity 913

Thus in B6 Hi-, the 7 MOs (mainly bonding in character) are remaining filled in and it is stable.
Thus the MO picture supports the Wade's rule. In the hypothetical species, B6H~-, the 15th electron
will go to the t2u MO which is antibonding in character and it explains its instability. In the neutral
species, B6H6 the 6 skeletal pairs will not be sufficient to fill in the 7 bonding MOs. Thus the neutral J

species, B,H, is expected to be less stable than B,H:-.

10.12.8 Carboranes and their Structural Features
Carboranes clusters contain both Band C atoms in the framework. Carbon possesses one more electron

ry
than boron, so Bn- is isoelectronic and isolobal with CH unit. These two isolobal fragments possess
the uppermost orbitals (Le. frontier orbitals) with the same symmetry. It is represented as follows:

ra
H H
p~~ID ~ID~

ib
orb~B~ • ~ c~ JH)~bitals
o
yl
0/7.~
sp/~
orbital
m ~ sp-orbital
he
Thus in boron hydrides, the BF fragments can be replaced by ~he CH units. Thus when two BF
units in BnH;- are replaced by two CH units, the electroneutral species C2Bn_2Hn is produc~d.
lc

-BH- BH-
B H 2- CB H- - )C B H
n n + CH) n- 1 n + CH 2 n- 2 n
ea

Thus, the carborane B4C2H6 is an analog of B6Hi- (cf. Fig. 10.12.8.1). BIOC2HI2 is related with
th

B12H122- ·
The carboranes also obey the electronic rules as in boranes and they can also exist as in closo-,
cn
e/

nido- and arachno series. In calculating the number of skeletal electrons (cf. Sec. 10.12.9), each
group contributes three electrons for framework bonding. The different forms may be related in a
t.m

redox couple, e.g.

closo - C2B9H 11 + 2e ~ nido - C2B9H121-
+2e. +2e
Le. c/oso - ) nldo - ) arachno-
c/oso-compounds can be converted into nido-compounds by the action of a Lewis base (acting as 2e
donor).
c/oso-C2B4H 6 +NR3 ~nido-C2B4H6(NR3)
./

Similarly, nido-compounds can be converted into the hypho-compounds by the addition of Lewis
bases on the electron deficient bonds.
nido:..BsH9 + 2PMe3 ~ hypho-BsH 9(PMe 3)2
This hypho-compound is the first well characterised boron hydride in hypho-series.
914 Fundamental Concepts of Inorganic Chemistry

ry
ra
ib
yl
m
he
lc
ea
th
e/
t.m

1.2-B10C2H12 1.7-B10C2H12 1, 12-B10C2H12

(Ortho-carborane) (Meta-carborane) (Para-carborane)

Fig. 10.12.8.1. Some representative structures of neutral closo-carboranes and their respective closo-
B"H~- (0 for B, • for C, • for 1-1).

c
10.12.9 Calculation of Skeletal Electron Pairs (S) In Carboranes [(CH).(BH)pHq+cl +
Out of the four valence electrons of C, one is involved in .making the CH bond, and the three are
remaining for skeletal bonding. The framework electron counting is done as follows :
3 1
2" electron pair from each CH unit + 1 electron pair from each BH unit +"2 electron pair from
1
each extra H + - 2" electron pair for each + charge.
 Covalent Compounds: Characteristics, Structure and Reactivity 915

Thus the total number of skeletal pairs (S) in [(CH)a(BH)pHq+,:f+ is given by :

3 1 1 1· 1
8=-a+ p+-(q+c)--c=(a+ p)+-(a+q)=n+-(a+q)
2 2 2 2 2
The number of vertices of the polyhedron is given by n (= a + p), and the extra hydrogens are
distributed in 3c-2e B-H-B bridge bonds and in additional B-H (2c-2e) terminal bonds.
The series are characterised as follows:
8 = n + 1 (closo-series), = n + 2 (nido-series), = n + 3 (arachno-series), where n = a + p.

ry
Illustration: C"BsH1'" Le. (CH)2(BH) sH2 gives the values: a = 2, P = 8, q = 2, C = 0, n = a + p = 10,
I 1
S = n + 2" (a + q) = 10 + 2" (2 + 2) = 10 + 2 = n + 2. Th,us it is having the nido-structure. In C1,BIl"

ra
1
Le. (CH)2(BH)4' a = 2, p = 4, q = c = 0, 8 = 6 + 2" x2 = 6 + I, Le. it is a closo 'compound. Similarly,

ib
~"B3H7' is 1,2-dicarba-nido-pentaborane(7) and the heteroborane PB 11 H 11, can be named as
phospha-closo-dodecaborane( 12) where the position of P is not required to be specified as all the

yl
icosahedral vertices are equivalent. m
Examples 0/ carboranes :
(i) Closo-series: C2B3Hs' C2B4H 6 , C2B sH7, C2BIc#I2 etc. These may be represented by (CH)2(BH)p
he
which is isostructural and isoelectronic with (BH)~-+2 e.g. C2B4H6 is isostructural and
isoelectronic with B6 H;-. .
lc

(ii) Nido-series: C2113H7 Le. (CH)2(BH)3H2 (isoelectronic with B sH9), CB sH9 Le. (CH)(BH) sH3
(isoelectronic with B6H 10 ), C 2B sH I2 Le. (CH)2(BH) sH 2 (isoelectronic with B Ic#I4)' CB9Hi;
ea

(isoelectronic with BI c#I4).

It is illustrated for B 1c#14.
th

- BH- + - BH- 2+
B
C~[:2H+ CN
e/

IO l4
nido-B H + CN ) ) C2 S[:2H+
t.m

nido-C~Hu nido-C2 BsHI 2

(iii) Arachno-series: 1,3-C2B7H I3 Le. (CH)2(BH)7H4 (only this example is known.)
3 1
SEPs = 2 x - + 7 + (13 - 9) x - = 3 + 7 + 2 =9 + 3.
2 2
C2B7H 13 is isoelectronic and isostructural with Bgll1S •

arachno-B9 H ls - 2BH- ) c Ii H 2+ - 2H+ ) C B7 H I3

2
+ 2CH 2 7 IS

For [(CH)a(BH)pHq+c]c+, the number of available v~lence atomic orbitals for constructing the
skeletal MOs is 3 (a + p) + (q + e) and at most'! {3n + (q + e)} where n = a + p bonding MOs can be
2
produced.
916 Fundamental Concepts of Inorganic Chemistry

Structures of some common carboranes are given in Fig. 10.12.8.1. In naming the carboranes, the
position of C-atoms is to -be mentioned, e.g. B4C2H6 is 1:6-dicarba-closo-hexal1orane (6).
Note : The generalformula of a neutral borane or hydroborate (i.e. anionic borane) or carborane
can also be expressed as follows :
[(CH)a(BH)pHq]C-
The number of electron pairs for framework bonding is given by :
3a 1 1
S=-+ p+-(q+c) =(a+p)+-(a+q+c)

ry
2 2 2
=n +.!. (a + q + c), n = no. of vertices
2

ra
Total AO's available fQr skeletal bonding = 3n + q.
1
Maximum no. of bonding skeletal MOts (possible) = "2 (3n + q).

ib
Conditions for different series :

yl
closo- : a + q + C = 2
nido- : a + q + C = 4
m
arachno- : a + q + C = 6.
he
10.12.10 Jemmls' Unifying Electron Counting Rule for Condensed Polyhedral Boranes
(Ref. E.D. Jammls et al., J. Am. Chem. Soc., 123, 4413, 2001; Chem. Rev., 102, 93,
lc

2002; Acc. Chem. Res., 36, 816, 2003)

Wade's skeletal electron pair counting rule (Sec. 12.8.5) is applicable only for monopolyhedral
ea

boranes. It states:
S = n + 1 + p, S = no. of skeletal electron pair; n = no. of vertices; p = no. of vertices missing Le.
th

p = 0 (closo-series), = 1 (nido-series), = 2 (arachno-series) for monopolyhedral boranes.

Jemmis' mno rule is applicable for both monopolyhedral (Le. m = 1) and condensed polyhedral or
e/

macropolyhedral (Le. m = 2, 3, ...) boranes. According to this mno rule:

t.m

S=m+n+o+p
m = number of polyhedra condensed; n = no. ofvertices; 0 = no. ofsingle vertex shared in developing
the macropolyhedral system; p = no. of vertices missing from the ideal polyhedra.
From Jemmis' rule, Wade's rule is obtained as a special case for the condition:
m = 1, 0 = 0 and p = 0 (cltJso), = 1 (nido), = 2 (arachno)
Jemmis' rule is applicable for polyhedral boranes, carboranes, metalloboranes and metallocenes. It
is illustrated in some representative examples:
• closo-BsHi- (hexagonal bipyramidal): m = 1, n = 8, 0 ~ 0, p = 0; Le. S = 9.
• closo-B1 4 H;i (condensation of 8sH;- through one edge sharing) : m = 2, n = 14, 0 = O,p = 0;
Le. S = 16.
• nido-B7 H~- (hexagonal pyramidal) : m = 1, n = 7, 0 = 0, p = 1 Le. S = 9.
 Covalent Compounds: Characteristics, Structure and Reactivity 917

• bis-nido-B12 Hfi (condensation of hexagonal pyramidal nido-B7 Hi- through one edge sharing):
m=2,n= 12,o=0,p=2Le.S= 16.
• arachno-B6 H;- (hexagonal planar) : m = 1, n = 6, 0 = 0, p = 2 Le. S = 9.
• bis-arachno-Bl0H~0- -(condensation of hexagonal arachno-B6 H2- through one edge sharing) :
m = 2, n = 10, 0 = 0, p = 4 Le. S = 16.
Note: In the above examples, it has been illustrated for the hypothetical hexagonal boranes, Le.

-BH 2+ -BH 2+

ry
closo-BsHi- ) nido-B7 H ll ) arachno-B6 H l2
+4H+ -2H+
(Le. B7H7 + 4) (Le. B6H6 + 6)

ra
Missing of Missing of
(Hexagonal one axial verttx
) (Hexagonal one axial vertex ) (Hexagonal

ib
bipyramidal) pyramidal) planar)

• (Cp)2Fe (ferrocene): m = 2, n = 11,0 = l,p = 2.

yl
Here condensation of two pentagonal bipyramids through the sharing of one axial position is
considered (Le 0 = 1). It leads to : m = 2, n = 11, 0 = 1, p = 2 Le. S = 16.
m
• Condensation of pentagonal pyramidal nido-B6Ht- through edge sharing gives the products
he
(Fig. 10.12.10.1) bis-nido-B1oH:-, tris-nido-BI4H~o.

nido-B6 Ht bisnido-B10Hr tris-nido-B14 Hfo

lc

S=m+n+o+p: 1 +6+0+ 1 =8 2+10+0+2=14 3 + 14 + 0 + 3 = 20

ea

Condensation.
th

of 2-unlts
e/

nido-BsHt bis-nido-B 10 Ht fa
tris-nido-B 14 H
________ ___ _ _ _ _ _J+
I condensation of
t.m

3 units
Fig. 10.12.10.1. Condensation of 86H:- units through the sharing of one edge.
• Condensation of two icosahedral closo-BI 2Hf2- (m = 1, n = 12, 0 = 0, p = 0) units through
sharing of one edge gives clos.o-B2oHI6 (m = 2, n = 20, 0 = 0, p = 0 Le. S = 22).

.10.13 SYNTHESIS AND REACTIVITY OF BORANES AND CARBORANES

10.13.1. Synthesis of Boranes
(a) BII6 is obtained by the reduction of boron halides.
8BFj + 6NaH ~ 6NaBF4 + B2 H 6 ; 4BCl3 + 3LiAIH4 ~ 3LiCI + 3AICl3 + 2B2 H 6
Note: BeCl2 on reduction by LiAIH4 produces Be(AIH4 )2.
918 FundamentaJ Concepts of Inorganic Chemistry

(b) Stock prepared boron hydrides by the acidic hydrolysis of magnesium boride. Many ~oranes are
hydrolysed in aqueous m.edia. This is why, Stock could isolate Blilo onl1 as it reacts with
water very slowly. B4H 10 on pyrolysis produces B2H6 and higher boranes.

2MgB2 + 12HCI + 4Mg --. B4 H 10 + 6MgCl2 + H 2

B4 H\0 ~ B2 H6 and higher boranes.
(c) Pyrolysis of B2H6 in a certain temperature range can produce different higher boranes which can

ry
be separated by fractional distillation under vacuum.
The boranes (Bjlp + q) can be formulated as (BH)n (BH3)x where n = 0, 1, 2, ...., 10; x = I, 2, 3
e.g. B2H6 == (BH3)2; B3H7 == (BH)(BH3)2; BsH9 == (BH)3(BH3)2; B 1cfi14 == (BH)s(BH3)2; B 1cfi16 ==

ra
(BH)7(BH3)3; in fact, x = 2 for nido-series, and x = 3 for arachno-series. During pyrolysis,
there is a gain or loss of BH3 units; and gain or loss of H2 (Le. BH3 --. BH + H2) and it can explain

ib
the route of conversion among the boranes. It is illustrated in the following examples:

yl
B3H9 --. B3 H 7 + H 2 ; 2B3H9 m --. 3B2H 6 ; B2H 6 + B3H 7 --. BsHll + H 2;
B3 H9 + B4 H 10 B2H 6 + BsH11 + H 2, etc.
--.

(d) The bridging H-atom in lower boranes is sufficiently acidic to be abstracted as a proton.
he
Thus the corresponding conjugate base anion bears the B-B bond which can act as the site
of insertion of the .electrophilic reagent like BH3• In fact, It" abstraction followed by the
insertion of a BH3 group can lead to polyhedral expansion. This allows the synthesis of higher
lc

boranes. It is illustrated in the following cases.

ea

B4 H 10 + KH ~ K[ B4 H9 l + H 2 ;
I H+
th

K[B4 H9 l + '2 B2H6 ~ K[BsH I2 l ) BsH l1 + H 2

1 .
e/

BsH9 + KH -+ K[BsHsl + H2; K[BsHsl + '2 B2H6 -+ K[B6H l1 l

H+
t.m

K[B6 H l1 l ) H 2 + B6 H 10

(e) The stable closo - B1oHto- and B12H122- are obtained as follows:

150°C 2
B10 H 14 + 2R3 N ---~) B10H1o- + H 2 + 2R3NH+
150°C 2
6B2 H6 + 2R3 N ----.) B12 H 12- + I1H2 +- 2R3 NH+

10.13.2. Reactivity of Boranes

(a) Combustion in air: The boron hydrides can bum explosively and their heat of combustion is
about 1.5 times higher than those of comparable hydrocarbons. This opens the possibility ofuse
of boranes as a rocket fueL However, the combustion product B 20 3 (solid) can block the
engine. -
 Covalent Compounds: Characteristics, Structure and Reactivity 919

(b) Thermal stability : In general, thermal sta~i1ity depends on the nature of boron hydri~s. The
thermal stability order is: closo- > nido- > arachno- > hypho-. In general, the higher boranes in
a particular series are less stable.
(c) Hydrolysis: All boron hydrides (except B 1oH14 which is solid and stable to air and water) are
unstable with respect to hydrolysis and the products are B( 011)3 and H 2 • However, the species
H:
like BIOH12o- and B12 2- are kinetically stable with respect to hydrolysis. In general, the closo-
boranes are less reactive than the nido- and arachno-boranes.
A

ry
B4 H 10 + 12H20 ~ 4B(OH)3 + IlH 2
(d) Reaction with the Lewis base (L) : Because ofthe electron deficient character, the boranes are

ra
expected to react with the Lewis bases. Depending on the nature of base, three important types
of reactions may occur. These are cleavage (both symmetric and unsymmetric), addition and

ib
bridging proton abstraction (Le. bridging hydrogens are acidic).
(i) Cleavage reactions are illustrated as follows :

~ /H" /H
B B + 2L ~

yl
2 LBH3 , (Symmetric cleavage)
H/ "H/ "H
m
~
he
V
H/~H/B"H
H
" /H
lc

B2H 6 + 2£ ~ 2LBH3 (symmetric cleavage)

ea

B2H6 + 2CO ~ 2H3 BCO; B2H6 + 2NR3 ~ 2H3 BNR3

B2H 6 + 2L ~ [L2BH2]+ [BHi], (unsymmetric cleavage for L = NH3)
th

The unsymmetric cleavage is mainly done by the small and hard Lewis bases (e.g. NH3)
e/

while the soft Lewis bases (with the bulky substituents) promote the symmetrical cleavage.

- /:t 0 ~
t.m

_ I"\. /H :L

Jr 1 rr "H
/K- L
(Symbiosis)
Unsymmetric cleavage

:LL Symmetric cleavage

The above mechanistic steps indicate that for the bulky Lewis base, attack on the same
B-centre at the second step is sterically disfavoured and it prefers the symmetric cleavage.
Small and hard Lewis bases like 011, NH3 lead to the unsymmetric cleavage where attack
on the same B-centre at the second step is favoured due to symbiotic and steric reasons.
Symmetric and unsymmetric cleavage of B4 H 10 are illustrated below.

B4 H 10 + 2L ~ [H 2 BL2 ]+ [B3 H g ]-, (L = NH3 , OH-, etc.) (unsymmetric cleavage)

B4 H 10 + 2L ~ LB3 H 7 + LBH3 , (L = Me3 N, ~O, Me3 P, etc.) (symmetric cleavage)
920 Fundamental Concepts of Inorganic Chemistry

ry
ra
ib
yl
The Lewis bases like NH), PMe 3, CO cleave the boranes as follows:
m
B4H IO + 2NH3 ~ [H 2B(NH3 )2l+ [B)HSl-
he
BsH I1 + 2NH3 ~ [H 2B(NH3 )2]+ [B4H 9 ]-

B6 H I2 + 2NH3 .-+ [H 2B(NH3 )2]+ [BsHlo ]-

lc

BsHIl + 2CO ~ H 3 BCO + B4H 8 (CO)

ea

B6 H I2 + PMe3 H 3 BPMe3 + BsH 9

~

(ii) Proton abstraction from the B-H-B bridging bonds is illustrated in the following examples.
th

BIO H I4 + OH- ~ Blo H I3 + H 20, (pKa = 2.7)

e/

B loH I4 possesses four bridging H-atoms which are acidic. KH can abstract the bridging protons
from B6H lo •.
t.m

B6 H IO + KH ~ K[ B6 H 9 l + H 2
In general the deprotonation process can ~e illustrated in the following way:

Here, a 3c-2e B-H-B bond is converted into a 2c-2e B-B bond. Thus, the electron count
and boron cluster remain unchanged. In fact; the deprotonation does not lead to any major
structural change. However, the electron rich B-B site in the deprotonated species can
react with the electrophiles to insert them into the bridging position. Insertion of a BH3
group to this B-B bond can lead to polyhedral expansion. This method can be utilised to
generate the higher boranes. This aspect has been discussed earlier.
 Covalent Compounds: Characteristics, Structure and Reactivity 921

The relative acidities of the bridging hydrogens are measured by considering the following
type of competitive reaction. 1

B10 H 14 + B4H; ~ B4H 10 + B10H o

The above reaction indicates that B1oH14 is more acidic than B4H 10 .
The bridging protons in nido- and arachno-boranes are quite acidic and the acid strength
sequence is given below:
Nido-series: BSHg (B6H 10 (B10 H 14 (B16 H 20

ry
Arachno-series: B4H)O (BsH 11 (B6H 12
Generally the higher boranes are more acidic than the lower boranes and the arachno-

ra
boranes are more acidic than the nido-boranes of comparable size.
The acid strength sequence can be qualitatively explained by considering the relative stabilities

ib
of their corresponding conjugate bases. The delocalisation of charge on the conjugate
base stabilises the species and greater the delocalisation, greater the acid strength (cf.

yl
methanol versus phenol).
(iii) Base addition may occur in the BHB bridging portions which are electron deficient. In fact,
m
the Lewis bases do not always lead to cleave the boranes. In some cases, the Lewis bases as
nucleophiles can attack the electron deficient BHB portion. In fact, formation of B2Hi
s
(from B2H6 ) or BsH (from BsH7 ) through the nucleophilic attack by Jr is well known.
he
Other examples are:
Nido - BSHg + 2PMe3 ~
Hypho - BsH9 (PMe3 )2
lc

B10 H 14 + 2L ~ H 2 + B10 H 12 (L)2' L = PR3 or CH3CN

ea

The compound, B 1oH12(L)2 is isoelectronic and isostructural with BIOH124- (which can be
obtained by the 2e-reduction of B 1oHI4). The chemistry of B 1oH12(L)2 is quite interesting.
th

~OH12L2 + 2R3 N ~ 2R3 NH+ + 2L + closo - B10 H)20- (very stable)

BIOHI2~ + HC == CH ~ BIOC2H12 (ortho-carborane) + H 2 + 2L; L = Et2S
e/

Different types of reactions are illustrated in Scheme 10.13.2.1 and Fig. 10.13.2.1 taking
B 1#14 as a representative example.
t.m

+2L,-H 2
(L = PR 3, RCN)

(BH),oH4 == B10H 14 (B10H12L2)

Fig. 10.13.2.1. Structure of B10H12~ (L = R3 N, R3 P, RCN, Et2 S) (0 for B, • for 1-1).

Note : The ligands (Le. L) bind with the borons at the open faces.
922 Fundamental Concepts of Inorganic Chemistry

2Et3N·BH 3
~~~~~~~~~~~~~~~[Et3NH]2 [B 12 H12],(Condensationand closu~ ~action

(-3H 2) leading to closo-B 12H?2")

ry
ra
ib
H H
I I

yl
?IB~B0\
H-B-t~B>-tYI )BH
m
\
H~B~~
\ 8
NaH,
(Base = OH-,
he
etc.)
/ \
H "H
lc
ea

(Reduction by Na) ,
th
e/

RX/AICI 3
t.m

2-RB 10H13 + 2, -4 -R2B10H12 + .

(Electrophilic substitution) (Substitution in the 1, 2, 3, 4 positions)
Scheme 10.13.2.1. Some representative reactions of B10 H14 Le. decaborane(14).
Note : • 8 10 H14 is highly stable and available in crystalline condition. It can be easily handled and
consequently its chemistry has been well studied.
• The distribution of electron density on the B-centre is not uniform. Electrophilic substitution
(e.g. Friedel-Crafts alkylation) occurs at the 1, 2, 3 and 4 position (preferential sequence 2,
4 > 1, 3) while nucleophilic substitution (e.g. attack by LiCH3 ) occurs on 6 and 9 position.

(d) Electrophilic substitutions: Electrophilic substitutions in boranes are well known. The
position of attack depends on the electron density at different sites. B)oH120- bears two types
of B-atoms - apical and equatorial (i.e. basal) but in icosahedral B12H122-' all positions are
equivalent (cf. Fig. 10.12.3.3). Molecular orbital calculation indicates that the electron density
on B-centre runs as follows :
apical- B)oH)20- > equatorial- B 10 H)20- ~ B 12 H)2;
 Covalent Compounds: Characteristics, Structure and Reactivity 923

It explains the reactivity order: BIOHI2o- ~ BI2HI22-.

The electrophilic attack occurs more favourably on the apical B-side than on the equatorial or
basal B-site in B1oHto because of the higher electron density on apical boron. This
electrophilic substitution at the apical position leads to the kinetically controlled product.
At higher temperature, it may isomerise to a thermodynamically controlled product.
Friedel Crafts alkylation (Le. electrophilic substitution) on BSHg occurs at the apical B-site at
lower temperature and it occurs at the equatorial position at higher temperature.

ry
ra
ib
yl
m Nido-BSH g .

Fig. 10.13.2.2. Electrophilic substitution on BSHg Le. pentaborane(9).

he
The I-alkyl derivative is the kinetically controlled product and it is obtained at lower
temperature. But at higher temperature, the alkyl group migrates to the 2-position to give the
lc

thermodynamically controlled product.

Electrophilic substitution by halogens (in the presence of Friedel-Crafts catalyst, the reactivity
ea

order: Cl2 > Br2 > /2) is illustrated in the following examples:
BSHg + /2 ~ BsHs/ + H/
th

Here I-/BsHs (apical isomer) is the kinetically controlled product which can isomerise to
e/

2-/BsH s (equatorial isomer). The kinetic favour arises jrom the higher electron density at
the apical B-site.
t.m

B10 H I4 + /2 ~ BIOHI2/2 + H 2
BIOHI2/2 (2,4- or-I, 3-disubstituted product)
For B t oH14' MO calculation shows that the B-atoms at the positions 2 and 4 bear excessive
negative charge and B-atoms at 1 and 3 positions are almost neutral, while all other B-
atoms bear the positive charge. This is why, the 1,2,3,4 positions can be electrophically
substituted although the positions 2 and 4 are slightly preferred.
In fact, alkylation (Friedel-Crafts reaction) on B 10H I4 produces predominantly 2-RB 1oHI3.

BIO H 14 RX) 2 - RBIO H 13 (major product) + 1- RBIO H 13 (minor product)

Aiel)
(e) Hydroboration : Hydroboration reaction considers the addition of diborane to the alkene$
and alkynes in the solvents like either, tetrahydrofuran, etc. in N 2 atmosphere. The reaction
involves the anti-Markownikoffaddition ofthe fragments Hand BH2 groups and the product
is cis (s)'n). These hydroboration reactions are highly important in organic synthesis and
924 Fundamental Concepts of Inorganic Chemistry

these were mainly developed by Prof. H.e. Brown and for this contribution, he was awarded
the Nobel Prize in 1979. Though Prof. Brown is now well known as an organic chemist, but
initially he was trained as an inorganic chemist. The hydroboration reaction is shown below:

I I
" /
/C=C"
BH3 -EI2 0
~ -T-f-
BH2 H

ry
ra
ib
yl
The trialkylboron (R 3B) is the final product when the starting alkene is sterically unhindered,
m
but for the sterically hindered alkenes, the reaction may stop at the R2BH or RBH2 stage.
B/l6
(Me)HC=CH(Me) ----i~~ (MeCH2-CHMe)3 B
he
Me" /Me
lc

/C=C,
Me H
ea

Me" /Me
/C=C,
Me Me
th

The alkyl or aryl boranes are converted into varieties of organic compounds in situ. Some
e/

illustrative examples are given below:

H+ NaOH,H 20 2
R3 B . ) 3RH; R3 B ~
3R - OH (alcohol)
t.m

protonolysis .
[0] NH2SOjH Br2
B(CH2 R)3 ---~ 3RC02 H; BR3 ) 3R - NH 2 , BR3 ) 3RBr
H 2Cr 04

(Norbornene)
(exo-2-norborneol) .
NH2

(exo-product)
 Covalent Compounds: Characteristics, Structure and Reactivity 925

In the above cases, the cis-hydroboration leads to the stereoselective reactions.

1. BJl6
R-CH=CH2 ~ R-CH-CH3 + R-CH2 -CH20H
2. H 20 2, OH I
OR
(R = bulky alkyl group) (Markownikoff (Anti-Markowni-
product, minor) koUproduct, major)

i~J

ry
6~H

ra
2.H20 2,OH-
( I-methylcyclo- (trans-2-methylcyclohexanol)

ib
, hexene) (Stereoselective product)

~
3H

yl
OH
H
2.H;02,OH-
m
(l-methylcyclo- (trans-2-methylcyclopentanol)
he
pentene) (Stereoselective product)
Mechanism of hydroI,oration involves the addition ofelectron deficient BH) (which actually
remains as BH)- solve"ilt adduct) to the double bond. BH) takes up the 7t-electron cloud to
lc

produce some sort of carbo-cationic character. Then the electron deficient C-centre attaches
ea

to a hydrogen atom of BB) to produce a cyclic transition state. Then within the cyclic transition
state, hydride transfer to the electron deficient C-centre produces the product. It may be
noted that in the case ofMarkownikoffelectrophi/ic addition ofHX to a double bond, hydrogen
th

adds as F. The cis-hydroboration leads to stereoselectivity.

'2 '2 12
e/

1/ . S+ 1/ S+ &-11
/c ~c"
+ BH] ----. /\:----,9, ----. -1---\-~-
, , . "'-.
t.m

',,' ;~:0+
6-BH3 0- H--BH 2
(I) (II)
In attaining the cyclic transition state (II), the carbocationic centre may arise either at C-I or
C-2 centre. The centre which is more substituted is the better candidate to develop the
carbocationic character. It explains the ..a .nti-Markowniko/f and cis addition of BBl.

S+ 0-
H C-CH==-==CH2
3 I
I
~II
I I

n-' -BH
I~

&--
I

S+ 2

(f) Substitution of BH fr~gment by isolobal organometallic fragments leading to metallo-

boranes : BSHg can react with Fe(CO)s to produce a metalloborane B4HsFe(CO») through
926 Fundamental Concepts of Inorganic Chemistry

the substitution of the apical 'BH vertex by Fe(CO)3 fragment. In fact, the BH and Fe(CO)3
moieties are isolobals. BH group provides one skeletal electron pair (SEP). Fe(CO)3 fragment
1
also provides 1 SEP = 2" (8 + 3 x 2 - 12)]
-BH
nido - BSHg + Fe(CO)s _ 2eO ) Bg H gFe(CO)3 (square pyramid)

ry
ra
ib
yl
m
10.13.3 Synthesis and Reactivity of Carboranes
he
Carboranes are obtained by replacing the BI1 groups by the isoelectronic and isostructural fragment
CH. Replacement of two BI1 units by two CHunits gives the neutral closo-carboranes. For example,
lc

addition of C2H2 to B 1oH14 in presence of Lewis base Et2S produces closo-l,2-BlOC2H12 (1,2-dicarba-
closo-dodecaborane). The Lewis base (L) adds first to the electron deficient BHB bridging portions to
ea

produce the adduct B 1oH12(L)2 with the release of a molecule of H2-gas. The compound B 1oH12(L)2 is
isoelectronic and isostructural with BIOH124-.
th

B10 H 14 + 2Et2S ~ BIOH12(Et2S)2 + H 2

(Lewis base addition)
e/

BIOH12(Et2S)2 + C2H 2 ~ 1,2 -C2BIOH12 + 2Et'J.S + H 2

t.m

In general, the most common preparative route involves the reaction of boranes with acetylene.
500-6000 C
BSHg +C2H 2 ------+) 1,5-C2 B3 H s +1,6-C2 B4H 6 +2,4-C2 BsH7 ,(closo-products)
(-H 2 )

-- 200°C
BSHg + C2H 2 ) 2,3 - C2B4H g , (nido-product)
At low temperature (-- 200°C) nido-products predominate while at higher temperature (-- 500-6000 C),
the closo-products predominate. It indicates the higher stability of the closo-products.
Et2S
B10 H 14 +C2 H 2 ) 1,2-C2BIOH12
(-H 2 ) .

(Note: The chemistry of B1oH14 which is fairly stable has been studied rather extensively. By
adding a 'C-C' handle on the open face ofthe decarborane 'basket' (nido-structure), the closo-dicarborane
(Le. C2B 1oH12) 'is obtained and it earned the attention of chemists. In fact, this carborane is highly stable
 Covalent Compounds: Characteristics, Structure and Reactivity 927

and its property has been extensively studied. Thus closo-C2B1oH12 and the precursor (from the standpoint
of synthesis) nido-B 1oH14 are well characterised and well studied).
Depending upon the relative positions of the two C-'centres in the icosahedral framework, three
isomers of BIOC2Hl2 are possible. The 1,2-isomer (called ortho-isom~r) obtained in the above process
can be thermally converted into the 1,7-isomer (called meta-isomer) and 1,12-isomer (called para-
isomer). The isomers are shown in Fig. 10.13.3.1.

ry
ra
400- 500°C
•

ib
yl
12
(1,2-Carborane (1, 7-Carborane
Le. ortho-carborane) Le. meta-carborane)
m
he

The isomerisation leads to the most stable para-carborane.

lc

400-S00o C -700°C
ortho-carborane ) meta-carborane - - - - - + ) para-carborane
ea

(Le. I,2-carborane) (Le. 1,7-carborane) (I, 12-carborane)

(isomerisation of C2B u#12)
th

For the isomerisation, ortho ~ meta, the DSD (diamond-square-diamond) mechanism is very
often argued. In the DSD mechanism, the icosahedron structures of 0- and m-isomer remain in a dynamic
e/

equilibrium via a cubo-octahedron. The icosahedrons are produced by reclosing the square faces of
the cubo-octahedron. The cubo-octahedron is produced from the icosahedron through the opening of ~
t.m

pair of adjacent triangular faces into a square face. This is illustrated below:

It may be noted that the DSD mechanism cannot explain the meta ~ para isomerisation.
(Note: The C-centres in carboranes are the most electronegative centres (cf. 'Xp = 2, 2.1 and 2.5 for
B, Hand C respectively) and in the most stable isomer, there is a maximum separation between the
electronegative C-centres. This is why, 1,12-carborane is the most stable isomer).
• closo-hydroborate anions vs. closo-carboranes : Carbon being more electronegative than boron
polarises the B-e bond as ~+B-c&-. Compared to ~OHI2o-, the neutral carborane BIOC2Hl2 is much less
pron~ to the electrophilic attack. If, at all, an electrophilic attack occurs, it will occur on the B-centres
as far as possible away from the C-centres. It is understandable from the nafure of B-C bond
928 Fundamental Concepts of Inorganic Chemistry

polarisation. On the other hand, it is more sensitive than ~oHto- towards the nucleophilic atf4£k and
it will occur on the B-centres as close as possible to the electronegative C-centres.
The electron withdrawing inductive effect of carbon is reflected in' the acidity of carboxylic
acids of carboranes.
1,2 - HC(B10H10)C -C02 H(pKa = 2.S0)}
1,7 - HC(B10H10)C -C02 H(pKa = 3.0)
ct. C6 HsC02 H(pKa =4.2)
The carborane-carboxylic acid is stronger than benzoic acid. It indicates the better electron

ry
withdrawing inductive effect of the carborane cage (Le. B10CZ cage) compared to that of the phenyl
group. The higher acid strength of the 1,2-isomer compared to that of the 1,7-isomer is due to the

ra
better cooperative electron withdrawing inductive effect exerted by the two ortho-electronegative C-
centres compared to that in the meta-isomer.

ib
Reactivity of carborane BIOCzHIZ : The H-atoms attached with the relatively ~ore electronegative
C-atoms in C2B 1oH12 are slightly acidic. The acid strength of the CH-group runs in the three isomers

yl
as: ortho > meta> para (cf. effect of the cooperative inductive effects of two C-atoms). Such acidic
hydrogens may be replaced by Li+ when treated with n-butyl lithium.
m
B4H 6C2 + 2LiC4Hg ~ B4H 4C2 Li2 + 2C4H 10 ; Bl0HIOC2H2 + 2LiC4Hg'~ BIOHI0C2Li2 + 2C4H 10
The dilithiocarborane is a quite reactive nucleophile and Li may be substituted by many electrophilic
he
reagents. These are shown below:
lc

Li-C--C-Li H-C--C-H

\0/ \0/
ea

B10H10 B10H10

1 cO 2 + H20.
(Ortho-isomer)
th

B10H10C2(C02H)2 -RH1 +RMgX

e/

N Le. H-C--CMgX B10H10C212

UN H02C - C - - C - C02H

~ \0/ \0/ i.e.

I-\O/C-I)
t.m

B 10H 10
B10H10
( B10H 10

/F\COb
Fe(CO)5
• Ph2P PPh 2

c-c
I I
\0/
B 10H10

1,2-BIOH10C2H2 is quite stable but the B-atoms (i.e. 3 and 6 positions) adjacent to the C-atoms
are the centres olattack by nucleophilic reagents. It happens so because of the electron withdrawing
effect ofthe adjacent C-atoms which are the more electronegative centres. This is why, 1,2-B1oHI0C2H2
 Covalent Compounds: Characteristics. Structure and Reactivity 929

2- 2-

ry
ra
(a)
C2 BgH f1" (dicarbollide anion)

ib
yl
m
he
lc
ea
th

(b)
e/

[(TIS - 7,'8-C2B~H11)Fe]- [('1 5 - 7, 8-C2BgH11)2Re(CO)Jl-

(c) (d)
t.m

Fig. 10.13.3.2. Structure of dicarbollide anion and dicarbollide complexes. (a) Available orbitals projected
towards the missing B-atom in the open face of dicarbollide anion; (b) Pot-like structure of dicarbollide
anion; (c) Sandwich complex of Fe(lI) with the carbollide anion; (d) Re-complex with dicarbollide anion.
(0 for BH• • for CH)

experiences nucleophilic attack by the strong bases like 0](, with the removal of a BH2+ unit. It gives
a nido-carborane anion. Thus one of the B-atoms (either from 3 or 6 position) is lost as B(OR)3 (when
treated with OK).
c/oso -1,2 - C2BIOH12 + NaDEt + 2Et - OH ~ nido -7,8 - C2B9H l-2 + B(OEt)3 + H 2 + Na+
NaH can abstract one more proton from 1,2 - C2B9H l-2 to produce another nido-carborane dianion
(cf. Fig. 10.13.3.2).

C2B9H l-2 + NaH ~ Na+ + H 2 +nido-7,8-C2B9H121- (dicarbollide anion)

930 Fundamental Concepts of Inorganic Chemistry

This nido - C2B9H121- is a quite strong base and itmay readily recombine with the F ion to give
back the species like C 2 B9 H 12 , C 2 B9 H I3 (a neutral nido-carborane).
2- H+ - H+" Heat
C2B9H II ) C2B9H I2 ) C2B9H I3 ) 2,3 -C2B9H lI + H 2
closo-I,7-C 2B loH I2 (Le. meta-isomer) can also behave in the same way to produce
nido - 9,11- C2B9HI21-. In this isomer, the B-centres adjacent to C-centres are to receive the
nucleophilic attack.

ry
The nido - C2B9H121- (obtained from ortho- and meta-carborane) is quite interesting. This II-vertex
dianion provides a pentagonal C2B3 open face. It gives the pot-like structure (Fig. 10.13.3.2) and this
is why, it has the trivial name dicarbollide (Spanish olla meaning pot). In the open face, all the 5-atoms

ra
may be considered to be sp3-hybridised. Each atom can provide one sp3-hybrid orbital to generate five

ib
5-centred MOs in which 6-electrons are accommodated as in Cp- i.e. CsH; (cyclopentadienyl anion).
It is important ~o note that C2B9H121- can act as a 6e-donor (cf. BH2+unit has two valence electrons).

yl
Thus, these two anions can provide 12 electrons which are required by Fe 2+ to attain the next inert gas
configuration of Kr (3d 6 --+ 3d 10 4s 2 4p6).
N
m
2C2BgH121- + FeC/2 2) [Fe("s -C2BgH ll )2]2- + 2CI-
he
(cf.2CsH; + FeC/2 --+ Fe("s -CSH S )2 + 2C/-)
In fact, the nido - C2B9H121- ion is isolobal with the ligand cyclopentadienyl (CsH;) which acts
lc

as a six-electron donor. Thus, the above Fe(II) complex is very much ~omparable with ("s - CsHs)2Fe
(known.asferrocene). Both the complexes experience reversible oxidation in air.
ea

[Fe II (Cp)2] ~ [Fe Ill (Cp)2]+ + e

th

[Fell(C2~Hl1)2]2- ~ [FeIII(C2B9Hll)2]- + e
Co(III) being isoelectronic (3rt) with Fe(II) also forms a similar metal complex [CollI (C 2B9H 11 )2]-.
e/

Symmetrical sandwich type complexes are formed by C2B9H121- with the metal centres like Cr(III),
t.m

Fe(III), Fe(II), Co(III), Ni(III), Ni(IV), etc.

In fact, nido - C2BgH121- binds in the same way in the mixed ligand complex like,
s s
Na[(" - CsHs )Fe (11 - C2B9H lI )]
The following dicarbollide complex has been prepared as follows :
C2B9H121- + Re(CO)s Br --+ ("s - C2B9H II )Re(CO)3 + Br- + 2CO
Carborane-siloxane polymer : Because of high thermal and oxidative stability of carboranes,
meta-BIOC2HI2 moiety has been incorporated into the backbone ofcarborane-siloxane polymer. Ortho-
derivative is not used to avoid cyclisation. The monomer R -e. . . C -R (R = -SiMe2---O--SiMe2Cl)
produced undergoes polymerization through hydrolytic condensation.
. ~ . (i) CI-SiMe 2 -O-SiMe 2 -Cl . ~. . ~
LIC~CLI .. [-SIMe2-C~C-SIMe2-0-SIMe2-]
(ii) Hydrolysis n