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Clusters and Catenation in P-Block: Allotropes of Carbon
Clusters and Catenation in P-Block: Allotropes of Carbon
Allotropes of carbon
Allotropes of boron
Part of one layer of the infinite lattice of - The construction of the B84-unit, the main building block of the
rhombohedral boron, showing the B12 icosohedral infinite -rhombohedral boron. (a) In the centre of the unit is a
building blocks that are covalently linked to give a B12-icosohedron, and (b) to each of these twelve, another boron
rigid infinite lattice atom is covalently bonded. (c) A B60-cage is the outer skin of
the B84-unit. (d) The final B84-unit can be described in terms of
covalently bonded sub-units {B12}{B12}{B60}.
+
H H H
H H C H N
B
H H H H H H
8 valence electron series
B2H6: The boron atom in BH3 possesses a vacant 2p atomic orbital that readily accepts a
pair of electrons from a Lewis base (L:). In the absence of a Lewis base, BH3 will
dimerise by the donation of a pair of B-H bonding electrons from one molecule into the
empty 2p orbital of the other. The two bonding electrons are now shared between
three atoms and a H-B-H bridge is formed.
:L
H
L = 2e- donor B H LBH3
H
BH3
H H H H
H B
dimerisation H B B
H
B H H H H
H
Number of atoms in bonding contact in B2H6 = 8
need 8 x 2 = 16e if all bonds are 2e/2 centre
Number of valence electrons = (2 x 3) + (6 x 1) = 12
all bonding contacts between pairs of atoms are not 2e/2 centre
Polyhedral Boranes
e.g. closo-[B6H6]2-
[B6H6]2- is an octahedral (Oh) cluster of 6 boron atoms, each of which is bonded to a terminal
hydrogen atom.
2-
H/B
B H
B B
z
sp hybridised x 6
H B
x H
SALC a1g + eg + t1u = 6 orbitals
B
px, py x 6 t1g + t1u + t2g + t2u
B
= 12 orbitals
y
t1u
LUMO t2u
This is a general result.
a1g
Boranes
Thus each H atom added (beyond the terminal B-H bonds) brings one electron to
the skeletal (B-H/B-B) cage.
B
H H
H H
B
B B
H
H H H
H
4 of the 6 hydrogen atoms bridge across B . . . . B edges
and two form terminal B-H bonds
Why do bridging hydrogen atoms occupy sites around the open faces of a cluster?
The open face of a cluster is generated by removing one, or more, vertices from a deltahedral cluster.
Considering MO theory, the loss of a vertex leaves a region of electron density focused around an open
face, hence protons will readily interact with the open face. This leads to B-H-B bridges around the open
face.
Bonding cluster MO
2-
derived from [B6H6]
H 1s
AO
Example 1. B10H14
Example 3. [B12H12]2-
Example 4. C2B4H6
(a) {BH}, {BR}, {CH}, {CR}, {NR+}; (where R is a one electron donor e.g.
alkyl, aryl, halogen atom)
Contribute 3 orbitals and 3 electrons for skeletal bonding
(b) {BR}, {AlR}, {GaR}, {GeR+}, {SR3+}; (where R is a one electron donor e.g.
alkyl, aryl, halogen atom)
Contribute 3 orbitals and 2 electrons for skeletal bonding
(c) {BH}, {Ge}, {Sn}, {N+}, {Bi+}, {Se2+}; (where each bare atom carries an
exo-lone pair of electrons.
Contribute 3 orbitals and 2 electrons for skeletal bonding
The structures of the Group 14 anionic clusters [E4]2- (tetrahedron, [E5]2- (trigonal bipyramid),
[E9]2- (tricapped trigonal prism) and [E9]4-(monocapped square antiprism)
[Sn5]2-
[Ge9]2-
2- 2+
Bi Bi Se Se
Isoelectronic
species
Bi Bi Se Se
D4h
[Bi4]2- 2+
[Se4]
[B12H11R]2- + 1,7-(CO)2B12H10
+ 1,10-(CO)2B12H10
water H2O
X2 [B12H12-xXx]2-
soluble
salts x = 1 to 12
X = Cl, Br or I
2-
[B12H12]
Electrochemical Hydride
oxidation
in MeCN
[B24H23]3- No reaction
The reactivity and stability depends on cluster size and the counter-ion. Ag2[B6H6] detonates upon
heating, but Cs2[B6H6] is thermally stable. [B10H10]2- and [B12H12]2- are hydrolytically stable in
aqueous acidic and basic solutions.
Substitution is electrophilic
Resistant to chemical oxidation
All sites are structurally equivalent
H2O
arachno-B4H10
CO or PF3
C2H2 100 oC