Black plate (329,1)
Chapter 12 . Electron-deficient borane and carbaborane clusters: an introduction 329
CHEMICAL AND THEORETICAL BACKGROUND
Box 12.9 Bonding in [B6 H6 ]2 –
In Section 23.5, we discuss the isolobal principle, and the orbitals remaining which are classed as its frontier orbitals:
relationship between the bonding properties of different clus-
ter fragments. The bonding in boron-containing clusters and,
more generally, in organometallic clusters, is conveniently
dealt with in terms of molecular orbital theory. In this Box,
we show how the frontier orbitals (i.e. the highest occupied
and lowest unoccupied MOs) of six BH units combine to
give the seven cluster bonding MOs in ½B6 H6 2 . This
closo-anion has Oh symmetry:
H 2–
B H
B
H B
B H If we consider the BH fragments as being placed in the
B
orientations shown in the structural diagram on the left,
H then the three frontier orbitals can be classified as one
B
radial orbital (pointing into the B6 cage) and two tangential
orbitals (lying over the cluster surface). When the six BH-
H units come together, a total of (6 3) orbitals combine to
give 18 MOs, seven of which possess cluster-bonding charac-
ter. The interactions that give rise to these bonding MOs are
After accounting for the localized BH bonding orbital (BH ) shown below. The 11 non-bonding and antibonding MOs are
and its antibonding counterpart, a BH fragment has three omitted from the diagram.
Once the molecular orbital interaction diagram has been electron pairs available, which will completely occupy the
constructed, the electrons that are available in ½B6 H6 2 seven bonding MOs shown in the diagram above. Relating
can be accommodated in the lowest-lying MOs. Each BH this to Wade’s rules, the MO approach shows that there
unit provides two electrons, and in addition the 2 charge are seven electron-pairs for a closo-cage possessing six cluster
provides two electrons. There is, therefore, a total of seven vertices.
Black plate (330,1)
330 Chapter 12 . The group 13 elements
n=5 n=6 n=7 n=8 n=9
Trigonal Octahedron Pentagonal Dodecahedron Tricapped
bipyramid bipyramid trigonal prism
n = 10 n =11 n = 12
Bicapped Octadecahedron Icosahedron
square-antiprism
Fig. 12.24 The deltahedral cages with five to 12 vertices which are the parent cages used in conjunction with Wade’s rules to
rationalize borane cluster structures. As a general (but not foolproof) scheme, when removing vertices from these cages to
generate nido-frameworks, remove a vertex of connectivity three from the trigonal bipyramid, any vertex from the octahedron or
icosahedron, a ‘cap’ from the tricapped trigonal prism or bicapped square-antiprism, and a vertex of highest connectivity from
the remaining deltahedra. See also Figure 12.27 for 13-vertex cages.
Worked example 12.8 Using Wade’s rules to predict a
structure
= BH
Suggest a likely structure for ½B5 H8 .
H H H
There are five {BH}-units and three additional H atoms.
Each {BH}-unit provides two valence electrons.
There is one electron from the 1 charge. Self-study exercises
Total number of cage-bonding electrons available
Refer to Figure 12.24.
¼ ð5 2Þ þ 3 þ 1 ¼ 14 electrons
¼ 7 pairs 1. Confirm the following classifications within Wade’s rules:
Seven pairs of electrons are consistent with the parent delta- (a) ½B9 H9 2 , closo; (b) B6 H10 , nido; (c) B4 H10 , arachno;
hedron having six vertices, i.e. ðn þ 1Þ ¼ 7, and so n ¼ 6. (d) ½B8 H8 2 , closo; (e) ½B11 H13 2 , nido.
The parent deltahedron is an octahedron and the B5 -core 2. Suggest likely structures for the following: (a) ½B9 H9 2 ; (b)
of ½B5 H8 will be derived from an octahedron with one B6 H10 ; (c) B4 H10 ; (d) ½B8 H8 2 .
vertex left vacant: [Ans. (a) tricapped trigonal prism; (b) pentagonal pyramid;
(c) see Figure 12.23; (d) dodecahedron]
Remove
one
vertex
The types of reactions that borane clusters undergo
depend upon the class and size of the cage. The clusters
[B6 H6 ]2 and [B12 H12 ]2 provide examples of closo-hydro-
borate dianions; B5 H9 and B4 H10 are examples of small
closo nido
nido- and arachno-boranes, respectively.
The three extra H atoms form BHB bridges along three The development of the chemistry of [B6 H6 ]2 has been
of the four BB edges of the open (square) face of the B5 - relatively slow, but improved synthetic routes (see equation
cage. The predicted structure of ½B5 H8 is: 12.79 and accompanying text) have now made the dianion
