⮚ Introduction

⮚ Boranes
⮚ Nomenclature
⮚ Classification
⮚ Wade’s Rules
⮚ Styx Numbers
⮚ Diborane
⮚ Structure and Bonding
⮚ Reactions
⮚ Carboranes
⮚ Synthesis and Reactions
⮚ Carborane Ligands
⮚ Metalloboranes
⮚ Metallacarboranes
⮚ Compounds with metal-metal multiple bonds
⮚ Polyoxometalates (Isopoly and Heteropoly acids)
❖ INTRODUCTION

Clusters are a collections of atoms or molecules which are intermediate in size between a molecule and bulk solid. They may have varied
nuclearities and stoichiometry. They can be considered as link between atoms, molecules and bulk material. The properties of clusters changes
with size. Metal clusters have metal-metal bonds. This chapter first deals with boron compounds and then gradually leads to clusters such
carboranes, metalloboranes, metallocarboranes and isopoly-heteropoly acids. These complex materials finds various applications in the synthesis
of various organic derivatives and industry.
❖ BORANES
Boron occurs naturally as borax Na2B4O5(OH)4.8H2O and as kerniteNa2B4O5(OH)4.2H2O. Some other ores of boron are Colemanite, Urexite and
Kernite. Borate minerals contain trigonal BO3 or tetrahedral BO4 units. Boron has two stable isotopes, 5B11 (80.4% abundance) and 5B10 (19.6%), of
which 5B10 has a very high neutron absorption cross section. Boron is a non-metal belonging to group 13 (III A) whereas the other elements of this
group show metallic properties. Thus the chemistry of boron is quite different from other elements of the group. Boron resembles carbon and
silicon in its tendency to form covalent compounds using its sp2 hybridized orbitals. No ionic compounds containing B 3+ cations are formed
because the energy of ionization is
⮚ Boron Hydrides or Boranes: Boron forms several hydrides known as Boranes, composed solely of boron and hydrogen bonds and may be
neutral or ionic. They are electron deficient species possess fewer valence electrons than are required for a localized bonding [Link]
chemistry was first studied by Alfred Stock. Typical boranes are B2H6, B4H10, B9H15,B10H14, and B20H16.
❖ NOMENCLATURE:
The nomenclature of boranes is somewhat simple. As mentioned before boranes exist as neutral and ionic species.
Neutral Boranes: For neutral boranes prefix di, tri etc. are used before ‘borane’ to indicate the number of boron atoms. The number of hydrogen
atoms are indicated by writing the Arabic numeral in the parentheses at the end. For example:

BH3 borane (3)

B2H6 diborane (6)

B3H7 triborane (7)

B4H10
B5H9
tetraborane (10)
pentaborane (9)

B5H11
BH6 10
pentaborane
hexaborane (10)
(11)

B10H16 decaborane (16)

It is to be noted that these names are based on the molecular formula and not on their structures. Generally the numbers in the bracket are not
written.
Anionic Boranes: For anions the name ends with ‘ate’ and the number of hydrogen and boron atoms are specified along with the charge. Example:
Na[B2H7] sodium heptahydrodiborate(1 -)
Ca[B3H8]2 calcium octahydrotriborate(1 -)

Na2[B2(C6H5)6] sodium hexaphenyldiborate(2 -)

Na2[B10Cl10] sodium decachlorodecaborate(2-)
Na2[B10H10] sodium decahydrodecaborate(2-)

Na[B10H9NH3]sodium amminenonahydrodecaborate(1-)
B10H8(NH3)2 diammineoctahydrodecaboron
[B10H7(NH3)3]+triammineheptahydrodecaboron(1+) ion
[B10H8(COOH)2]2- dicarboxyoctahydrodecaborate(2-) ion
Na2B4O7 sodiumheptaoxotetraborate(2-)orsodium
tetraborate
Certain prefixes such as closo, nido and arachno are used. This classification will also be discussed. Eg. Na2[B10H10] sodium decahydro- closo-
decaborate(2-),[B12H11Cl]2-chloroundecahydro-closo-dodecaborate (2-)ion.
Substituted Boranes:

2.2 CLASSIFICATION OF BORANES

Higher boranes or borane clusters possess deltahedral structures which are somewhat complex in terms of their 3c-2e bonding. A deltahedron is a
polyhedron that possesses only triangular faces, e.g., an octahedron. The boranes are mainly classified as:
1. closo-BnHn+2 (closo-Greek for cage), Closo pertains to the most symmetrical form that is a closed polyhedra

2. nido-BnHn+4 (nido-Greek for nest), nido has one of the vertex removed from a regular polyhedral; (n + 1)-cornered polyhedron.
3. arachno-BnHn+6 (arachno-Greek for spider web).Arachno is a higher version of nido, with most highly connected boron vertex on the open
face removed. Thus,the arachno form has two vertices missing; (n + 2)- cornered polyhedron.
4. Hypho- BnHn+8(Greek: net like): They have the most open clusters in which the B atoms occupy n corners on an (n + 3)-cornered polyhedron.
5. Conjuncto- BnHn+10(Latin: join together): They have structures formed by linking together of two or more of the above mentioned type of
clusters.
They can also be written as having the general formula BnHn 2‒, BnHn4‾, BnHn6‾, BnHn8‾, BnHn10‾ for closo, nido, arachno, hypho and conjuncto
respectively. That is formally subtracting the number of H+ ions from the formula to make the number of boron and hydrogen atoms equal.
❖ WADE’S RULES:

A set of rules were laid down by Kenneth Wade to predict the shape of boron clusters. These rules correlate skeletal structures of boranes,
carboranes, heteroboranes and their anions (closo, nido, arachno, hypho) with the number of skeletalelectron pairs present in them.
According to the rule suppose a cluster has say ‘n’ skeletal atoms (that is

the vertices) then it will adopt closo structure if it contains n+1 skeletal bonding electron pairs. Similarly, nido if n+2, arachno if n+3 and hypho if
n+4 skeletal bonding electron pairs respectively and so on.
To determine this one needs to know the number of skeletal electron pairs in a cluster which can be determined by following the electron count for
various donating units as given below. Each BH unit gives 2 skeletal bonding electrons B as such gives three skeletal electrons
Each C-H unit of a carboranecontributes 3 skeletal bonding electrons Each additional H furnishes 1 skeletal bonding electron
Ionic charges must be included in the electron count For borane clusters with other hetero-elements, C,
Si, Ge and Sn of a cluster is replaced with a BH unit; N, P and As with a BH2 unit and S andSe with a
BH3 unit for counting purpose
B H B H ¯ C B
5 9 2 7 2 10H12 C B H
2 9 112¯
5 BH = 5x2 2 BH = 2x2 = 2 CH= 3x2 = 6e 2 CH= 2x3=
=10e 4e 6e

4 H = 4x1 = 4e 5 H = 5x1 = 5e 9 BH= 9x2

BH= 2x10 =
=18e
2
0
e
14 e = 7pair 1(-) = 1e 26e = 13 pair 2(-) = 2e
n = 5; n+2 = 10 e = 5 pair n= 12; 26 e = 13 pair
nido n+1 =
closo n= 11; n+2 =

n = 2; n+3= nido

arachno
(MeSi)2B10H10 CPB10H11
2 MeSi = 2x3 = 6e Consider C≡BH; PB11H12 10 BH = 10x2 = 20e
Consider P≡BH2; B12H14 26 e = 13 pair 12BH =
12x2= 24e
n = 12; n+1 = closo 2H = 2e
26e = 13 pair; n= 12; n+1= closo
❖ STYX NUMBERS:
The Styx rules were given by Lipscomb to determine what type of bonds are possible for a given formula of boron hydride. It is assumed that one
B‒H bond is present for each boron atom.
i. The centre 3c-2e, B‒H‒B bond is labelled as ‘S’

ii. Closed or open 3c-2e B‒B‒B bond is labelled as ‘T’

iii. The 2c-2e B‒B bond is labelled as ‘Y’
iv The B‒H terminal bond (2c-2e) labelled as ‘X’ or simply we can say number of BH2units
The B‒B‒B bond may be open or closed but it is the closed bonds that are always considered.
❖ SYNTHESIS of DIBORANE(6)
Diborane(6), B2H6 is a gas and like most boranes it is air-sensitive and catches fire. It is spontaneously hydrolyzed by water into hydrogen and
boric acid.
One of the simplest method is hydride abstraction from BH4-.

BH4- + BX3 ½ B2H6 + HBX3- (X = Cl, Br)

3 NaBH4 + 4 BF3 2 B2H6 + 3 NaBF4
2 NaBH
4 + I2 B2H6 + 2 NaI + H2
At industrial scale diborane is prepared by reduction of BF3 with sodium hydride
B H + 6 NaF
2 BF3 + 6 NaH 2 6
Diborane acts as a very versatile reagent in synthesis of organoboranes. It also acts as a reducing agent for certain functionnal groups such as
nitriles and aldehydes.
2.6 STRUCTURE AND BONDING

In the earliest stages of decoding the structure of diboranemany errors and contradictions led to the establishment of the structure known today.
The imminent deficiency of electrons in their structural formula indicates that there cannot be conventional 2c-2e (two center-two electron, two
electrons are shared between two atoms) bonds. Thus in the efforts to rationalize the structure of boranes, earliest concepts of multicenter bonding
were developed. Languet-Higgins proposed the theory of 3c-2e (three center-two electron) bonds which greatly helped in the understanding of
bonding in boranes. This implies that a pair of electrons can share more than two atomic centers. The simplest borane i.e. diborane B 2H6, is two
electron short for bonding when compared with its electron-precise analogue C 2H6. Thus,diborane is two electron short of conventional 2c-2e
bonding. It was proposed that BH3 exists as dimer to form B2H6. This was later confirmed by X-ray diffraction studies. These studies revealed the
presence of terminal and bridging hydrogen atoms. The two terminal hydrogen on each boron atom formed the conventional 2c-2e bonds thus
utilizing eight electrons out of the total of 12 electrons. The remaining two H atoms are bridging in nature. They link together the two boron
centers (B-H-B) as shown below. The bridging bonds are electron deficient utilizing only 4 electrons and form 3c-2e bonds.
Various types of bonds found in boranes.
❖ CARBORANES:

Carboranes are large family of clusters which contain boron and carbon atoms. They are mixed hydrides of carbon and boron having electron
deficient molecular structure. The carboranes are considered to be derived from BnHn 2¯ by replacement of BH¯ unit(s) with isoelectronic (since C
atom has one more electron than B so CH moiety is
isoelectronic with BH¯) and isostructural CH unit(s).
Each C-H group is regarded as donating 3 electrons to the framework electrons. So a replacement of two BH¯ will give a neutral molecule
having general formula Bn-2C2Hn. Carboranes having n =5 to n = 12 are known. They have delocalized electrons in the boron framework having
one or more carbon atoms. Carboranes with higher boron content are dominant. The most studied boranes are B 10H102- and B12H122-thus for
carboranes the best studied system is C 2B10H12 that is isoelectronic with [B12H12]2-. Some other boranes and their corresponding carboranes are
listed below
pentaborane(5) B5H52- [C2B3H5],hexaborane(6)B6H62- [C2B4H6] heptaborane(7) B7H72- [C2B5H7], octaborane(8) B8H82- [C2B6H8],
nonaborane(9)B9H92- [C2B7H9] , decaborane(10) B10H102-[C2H8H10] dianions B11H112- [C2B9H11].
Similar to boranes,carboranes are also classified as closo, nido and arachno which can be regarded as derivatives of BnHn+2 (or related anion BnHn2¯),
BnHn+4 and BnHn+6 respectively.
i. Closocarboranes: General formula CxBn-xHn-x+2 bonded by n+1

skeletal pair of electrons. Eg. Most common with x=2, C2Bn-2Hn. One or both C atoms can be replaced by isoelectronic B¯ ion to give CBn-1Hn+1.
ii. Nidocarboranes: General formula CxBn-xHn-x+4 bonded by n+2 skeletal pair of electrons. Here also C can be replaced by B¯ or BH to give
compounds that have their skeleton isostructural with BnHn+4
iii. Arachnocarboranes: General formula CxBn-xHn-x+6 bonded by n+3 skeletal pair of
[Link] are structurally related to BnHn+6 (i.e. x
=0); for example C2B7H13 is related to B9H15 and B9H14¯
3.2 CARBORANE LIGANDS
The carborane anion or dicarbollide anion [B9C2H11]2−has been used as ligand and numerous studies have been done on its [Link] anion
forms sandwich compounds with many metal ions known as bis(dicarbollides). When the 1,2-and 1,7-dicarba-closo-dodecaboranes are heated
with alkoxide ions, degradation of parent carborane occurs to form isomeric nidocarborane anions (B9C2H12)−.
4.0 METALLOBORANES
Compounds in which metal atom bound with boron hydride group form the class of compounds known as metalloboranes. They can be classified
into following categories:
1. Ionic hydroborates: Such as NaBH4, Ba(BH4)2
2. Metal hydroborates: Contain hydrogen bridge bonds, M‒H‒B. Eg:
Al(BH4)3, (Ph3P)2CuBH4.
3. Metal Carbaboranes: Include π-bonded ‘sandwich compounds’.
4. Compounds containing metal-boron bonds except those in the above category (3).
Like boranes and carboranes, metalloboranes can also be structurally classified as closo, nido, arachno, crypto and commo. Some of them are
depicted below.
METALLACARBORANES
Metallacarboranes or metallacarboboranes are metal complexes where carboranes or heteroboranes act as ligands with at least one metal atom
incorporated in the cage framework. They are inorganic polyhedral clusters which contain carbon, boron, hydrogen and metal ion in different
combinations. Hawthorne and co-workers first synthesised metallacarboranesin the mid-1960s. A typical example of metallacarborane is the
[C2B9H11]2− (dicarbollide) cluster having a metal atom sandwiched between two dicarbollide units. Here the dicarbollide, binds as η 5, thus
considered to be isolobal with cyclopentadienyl ligand, somewhat similar to ferrocene. Hawthrone suggested that [C2B9H11]2−is isoelectronic with
C5H5¯ and therefore it should be capable of acting as
There are two different types of metallacarboranes, endo- and exo. In endo- type the metal centre is sandwiched between two carborane clus

The other highly investigated metallacarborane is nido-[2,3- R2C2B4H4]2(R=H or a cage carbon substituents), having pentagonal bipyramidal
structure.
SYNTHESIS
1. Preparation of [C2B9H11]2− (dicarbollide)

2. Preparation of metallacarboranes
❖ COMPOUNDS WITH METAL-METAL MULTIPLE BONDS:

Metal clusters are those compounds which have metal-metal bonds. They are as old as chemistry itself. The halide and oxide metal clusters will be
discussed here. In these clusters the metal ion is in higher formal oxidation state +2 to +3 and frequently comprise of transition metals on the left
side of periodic table (early second row and third row of transition metals). Such as Zr, Nb, Tc, Ru, Rh, Hf, Ta, W, Re, Os, Ir and Pt.
The d orbitals play a crucial role in the formation of these clusters since effective

overlap of d orbitals is necessary for the stability of metal cluster. Contraction of d orbitals will cause destabilizing effect on the cluster. It is
owing to these reasons that the transition metals of first row even in +2 or +3 oxidation states are unable to extend the d orbitals sufficiently for
effective overlap.
⮚ Dinuclearcompounds:
A typical example of dinuclear metal compound is [Re2X8]2- ion. It can be synthesized as shown below. Reducing agents such as H2, H3PO2 or
PhCOCl can be used. The ion is formed as a royal blue colored product.

This compounds shows two very interesting structural features. Firstly, the Re-Re distance in the compound is 224 pm which is shorter than the

average Re-Re distance in rhenium metal (at 275 pm) or in Re 3Cl9 (248 pm). Secondly, the chlorine atoms are present in eclipsed configuration at
330 pm from Re which less than the sum of their van der Waals radii (340-360 pm). So, in such a situation a staggered form would be preferable.
Both the above features were explained by F. A. Cotton by proposing a quadruple bond.
❖ POLYOXOMETALATES (ISOPOLY AND HETEROPOLY ACIDS): Acid catalysis is an important area of heterogeneous catalysis.
Among several acid catalysts polyoxometalates(POM) also known as heteropoly
acids (HPAs) hold an important position owing to their catalytic properties. HPAs are used as catalysts in different reactions as acid, redox and
bifunctional catalysts in homogeneous and heterogeneous reaction systems owing to their high solubility in polar solvents and thermal stability.
They are also used as heterogeneous and homogeneous catalyst in medicine as antiviral and antitumoral agents.
⮚ THE ISOPOLYOXOMETALATES OR ISOPOLY ACIDS:
Some important isopolymetalates are discussed in this section. The basic unit of isopolychromate is CrO 4tetrahedra . They exist both in solution &
as solids. Chromates are stable only at high pH, on lowering the pH protonation anddimerisationoccursand (Cr 2O7)2-. In acidic solution (Cr2O7)2-,
predominates whereas in basic solution (CrO4)2- predominates.

The CrO3 structure consists of infinite linear chains of CrO4 tetrahedra.

There are certain reports of polymerization such as the Tri chromates (Cr3O10)2- and tetra chromates (Cr4O13)2- . Polymerization does not go
beyond (Cr4O13)2- .These anions as well as dichromate ion are formed by corner sharing CrO 42-tetrahedra. The tendency for Cr to form large
number of polyacids is limited. The small size of Cr6+ evidently limits it to the tetrahedral rather than octahedral coordination with oxygen.
⮚ THE HETEROPOLYOXOMETALATES:
Their general formula is [XxMmOy]n-(x ≤ m); M isusually Mo or W and sometimes V, Nb or Ta. X is the heteroatom which may be located at the
centre of [Link] heteroatom can be any ele”ment in the periodic table some of the most frequently encountered ions are P 5+, As5+, Si4+,
Ge4+, B3+ etc.
Heteropolyanion are by far mostly important for catalysis and other applications hence they will be discussed in detail. Molybdenum and tungsten
polyoxometalates are extensively studied and most easily formed because of the accessibility of their d orbitals forming metal-oxygen π
[Link] structure ofthe related phosphotungstate anion was determined in 1934, and is generallycalled the Keggin structure after its discoverer.
In the period following thisother fundamental structures, e.g. the Wells- Dawson ion, were discovered,and their chemistry and applications as
catalysts were determined.