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CHEMICALCOMMUNICATIONS,
1971

792

The Structural Significance of the Number of Skeletal Bonding Electron-pairs

in Carboranes, the Higher Boranes and Borane Anions, and Various
Transition-metal Carbonyl Cluster Compounds
By K. WADE

Published on 01 January 1971. Downloaded on 30/04/2016 10:05:29.

(Chemistry Department, Durham University Science Laboratories, South Road, Durham)

CH+ unit. Formally adding BH (or CH+) to B,Hma- to

has the same
convert it into Bm+lHm+lz- (or CB,H,+,-)
effect on the positions of the original m boron atoms as has
the addition of a pair of electrons to B,Hma- to convert it
into B,H,4-.
I n each case, the original m boron atoms
move to m of the m + 1 corners of the next higher polyhedron.
Species incorporating cage atoms other than carbon and
boron can be treated similarly. For example, a Group V
THREE
classes of structure are known for carboranes, higher atom (P, As, or Sb as in CB,,H,,P) with no terminal
boranes and borane anions.1 (i) Closo-structures are hydrogen attached contributes three electrons for skeletal
adopted by compounds C,B,H,+,
(a = 0-2).
Their n bonding, retaining a lone pair; accordingly, CB,,H,,P
(n = a + m) skeletal carbon and boron atoms occupy all adopts a closo-structure.
The structures of many transition-metal carbonyl cluster
the corners of the following polyhedra: n = 5, trigonal
bipyramid ; 6 , octahedron; 7, pentagonal bipyramid ; 8, compounds which are difficult to describe in other terms can
dodecahedron; 9, tricapped trigonal prism ; 10, bicapped be rationalised simply using this approach, For example,
Archimedean antiprism ; 11, octadecahedron ; and 12, consider the octahedral anion Ru,(CO) 182-, effectively the
icosahedron. (ii) Nido-structures are adopted by com- parent species from which the carbonyl hydride H,Ru,pounds C,B,H,+,
(a = 0-4).
Their n skeletal atoms (CO)18, containing six terminal Ru(CO), groups, is derived.5
occupy all but one of the corners of the (n 1)-cornered If we allocate eighteen electron-pairs to localized two-centre
polyhedron. (iii) A rachno-structures are adopted by com- Ru-C bonds resulting from overlap of 18 carbonyl carbon
pounds CsB,H,+,
(a = 0-6).
Their n skeletal atoms sp orbitals with 18 suitably directed metal orbitals (three on
occupy all but two of the corners of the (n 2)-cornered each metal) we are left with 36 metal orbitals (six on each
polyhedron.
metal), and 25 electron-pairs, for cluster metal-metal
All these species can be regarded as having the general bonding. Since not all 25 electron-pairs can be accomformula [(CH),(BH),H,Ic- and as being built up from a modated in orbitals that are strongly cluster bonding, it is
CH and m BH units, held together by the skeletal bonding realistic to allocate three electron-pairs per metal atom to
electrons they themselves provide (three from each CH unit, essentially nonbonding atomic orbitals (chosen to have
two from each BH unit), together with an electron apiece appropriate symmetry for dative n-bonding to the terminal
from the extra b hydrogen atoms, and a further G electrons carbonyl groups). This leaves seven electron-pairs for
in the case of anions.2a The total number of skeletal cluster bonding orbitals derived from interactions between
bonding electron-pairs is then 3(3a + 2m
b + c) = n the remaining three AOs on each metal atom. The picture
&(a b
c). The following generalisations hold. (i) this gives of the cluster bonding of Ru,(CO),,~- is directly
Species with (n
1) pairs of skeletal bonding electrons (a + analogous to that given by Longuet-Higgins3 for the anion
b + G = 2) adopt cho-structures. (ii) Species with (n + 2) B,H[,-.
Each Ru(CO), unit of Ru,(CO),,a-, like each BH
pairs of skeletal bonding electrons (a + b
G = 4) adopt
unit of the closo-borane anion, effectively contributes two
nido-structures. (iii)Species with (n 3) pairs of skeletal electrons, and three orbitals, to the cage bonding, for which
bonding electrons (a b G = 6) adopt arachno-structures. seven electron-pairs are needed to fill the seven bonding
These generalisations are valid because the symmetries of molecular orbitals.
the fundamental polyhedra are such that, in each case,
A similar treatment is possible for the related carbonyl
(n 1) bonding skeletal MOs result from interactions carbide RU,(CO),,C,~with the modifications that two 2between the three AOs contributed by each of the n skeletal centre bonds to a doubly bridging carbonyl group replace
atoms located a t their corners, as has been shown by MO two terminal Ru-CO links, and the central carbide carbon
treatments2bs3e4and because, if, when one or two BH2+(or contributes four electrons for skeletal bonding. For
CH+) units are removed from a closo-species and replaced Rh,(CO),,, the environment of the metal atoms is different,
by two or four H+ ions, the number and symmetries of the each being co-ordinated to two terminal carbonyl groups
skeletal bonding molecular orbitals will be unaffected if and two triply bridging carbonyl groups in a distorted
the H+ ions are located in sites that reflect the skeletal t e t r a h e d r ~ n . ~Allocation of an electron-pair to each of the
symmetry. These sites are generally BHB bridging sites, 24 Rh-C links uses four orbitals on each metal atom and
occasionally terminal sites, generating BH, groups (as in leaves altogether 30 atomic orbitals, and 19 electron-pairs,
B4H1, or B,Hl1) or CH, groups (as in C2B7H,,).
for use in cluster bonding. An apt allocations is of two
The progressive cage-opening that accompanies formal electron-pairs per metal to nonbonding (metal-carbonyl
addition of electron-pairs to a closo-species B,Hm2- occurs dative .rr-bonding) orbitals, leaving again three atomic
because one pair of electrons is precisely the contribution orbitals on each metal, and altogether seven electron-pairs,
made to skeletal bonding by a neutral BH unit or a cationic for cluster bonding.
Summary The skeletal structures of carboranes, the higher
boranes and borane anions, and many transition-metal
carbonyl cluster species are related to the number of
skeletal bonding electron-pairs they contain ; species With
n skeletal atoms adopt closo-structures if held together
by (n + 1) pairs, nido-structures if held together by
(n + 2) pairs, and arachno-structures if held together by
(n + 3) pairs of skeletal bonding electrons.

+
+

+ +

+ +

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Published on 01 January 1971. Downloaded on 30/04/2016 10:05:29.

CHEMICALCOMMUNICATIONS,1971
The analogy between these closo-octahedral carbonyl
complexes and the borane anion B,HS2- can be extended by
considering the compound Fe,(CO),,C, which has a square
pyramidal arrangement of five Fe(CO), units, the carbide
carbon being located below the centre of the base of the
pyramid., Removing this carbon atom without the
electrons it contributes to the cluster bonding, i.e. as C4+,
one is left with the square pyramidal anion Fe,(C0),,4-, the
nido-structure of which (cf. B5Hs4-as represented by BsHB)
is that appropriate for a cage species with five cage atoms
and seven cage bonding electron-pairs.
Other nido-species based on an octahedron, and incorporating both main group and transition elements as skeletal
atoms, are the iron carbonyl complexes Fe3(CO),S2,1*
Fe3(CO),Se2,11
and Fe3(CO),(NN:CPh&,12while the complex
Co4(COf10(C2Et#3is a further example of a doso-octahedral species. An extensive range of doso-species is of
course represented by metallocarboranes with seven [e.g.

793
(qB4H,)Fe11(CO)3],14nine C8.g.(~B,H,)CoUr(rr-C,H,)1,16
ten
[e.g. ( ~ B , H , ) C O ~ ~ ( ~ - C ~or
H ,twelve
) ] ~ ~ , [e.g. (GBsHll)F~III(v-C,H,)]~~
skeletal atoms, the examples cited showing
the group M(n-C5Hs), like M(CO),, to be capable of contributing three metal orbitals of appropriate symmetry for
cluster bonding. Significantly, when fewer orbitals are
available, as in bis(dicarbol1ide) complexes M(C,BgHl&~-,
in which M has eight (e.g. NiU)I8or nine (e.g.C U U )electrons
~
to accommodate in non-bonding orbitals, the metal is
displaced from the normal icosahedral position.
These examples illustrate the value of a common approach
to the skeletal bonding of cluster species in which the cluster
bonding orbitals result from interactions between three
atomic orbitals of each cluster atom. Further structural
examples can be found in recent
I thank Dr. A. J. Banister for helpful discussions.

(Received, April 14th, 1971; Corn. 549.)

E. Williams. Inore. Chem.. 1971. 10. 210.

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