Group No. 4

Presentation Topic
Poly Acids & Metal Cluster
Submitted to
Mr. Khalil Butt
Presented by
Naila Sehar Maryaam Tariq Nouman tariq

20014107-024 20014107-037 20014107-028
Zeeshan Ashraf Nouman tariq Amara Aslam

20014107-044 20014107-028 20014107-036
1
TABLE OF CONTENTS
Sr no. Sub-topic Slide
No
1 Introduction to Polyacids 3
2 Iso polyacids 5
3 Types of Iso polyacid 6
4 Structure of Polyacids 19
5 Heteropolyacids 9
6 Structure, Preparation and 22

properties of Heteropolyacids
7 Types of Heteropolyacids 27
8 Metal Cluster 33 2
Introduction to Poly acid
The weak acids formed from the amphoteric metals of group IB and VIB of
the periodic classification are characterized by the ease with which they
condense to form anions containing several molecules of the acid
anhydride.these are called poly acids.
Example:
The formula of molybdates in alkaline solutions are represented by
R2O.nMoO4 whereas in acid solution the formation of more comples anions
take place which are represented by R2O.nMO4.where n=1,2,3,4,8,10
depending on ph of the solutions.
3
Reference:
Types to Poly acid
There are two types of poly acids.
• Isopoly acids
• Heteropolyacid
4
Isopoly Acids
Isopoly acids are inorganic acidic compounds that form from

the combination of acids or anions of the same type. In this
formation process, a water molecule is eliminated during the
combination of two acids or anions. Some
For example:
Examples of isopoly acids include isopolychromate,
isopolymolybdate, isopolytungstate, isopolyvanadate,
isopolyniobates, etc.
Reference: 5
Inorganic Polymers – James E. Mark; Harry R. Allcock; Robert West
Types of Isoployacids
1. Isopolymolybdates:
There are different types of isopolymolybdate.
• Dimolybdates:
Their composition is R2O.2MoO3 nH2O.They are formed
when the solution containing sodium molybdates is
adjusted to 6.
• Paramolybdates:
These are the most stable polymolybdate in solution.they
are obtained by crystalising a solution containing sodium
molybdate at a at a Ph of 4.5.The structure of this ion has
been confirmed by X.ray diffraction.
Reference:
Inorganic Polymers – James E. Mark; Harry R. Allcock; Robert West 6
Cont….
● Octamolybdates:
There composition is R2O.MoO3.nH2O.they are prepared by treating
concentrated solution of alkali molybdates with 1.75 moles of
hydrochloric acid per moles of normal molybdates.there are some
evidence of this form.
Reference:
7
Cont….
2. Isopoly Tungstate
Like molybdates numerous tungstate of the metals have been described differing in
their R2O: WO3 ratio. The PH of tungstate is highly alkaline about 9
For example:
Tungsten trioxide is dissolved in a basic solution like NaOH or KOH, as a result
Normal Tungstate is formed.
WO3 + 2NaOH Na2 WO4 + H2O
It can easily crystallized by the aqueous solution and the tungsten
ion which is WO4.
Reference: 8
Cont….
There are different types of isopolymolybdate.
• Paratungstate A:
Paratungstate is an type of Isopoly tungstate. An example of Paratungstate A is
W7O24. it is prepared by hydrochloric acid to boiling solution of Na 2WO4.
• Paratungstate B
Paratungstate-B is also known as Dodecatungstate. It is derived from alkali
metal salts of normal tungstate upon their acidification. An example of
Dodecatungstate is [H2W12O24 ] .
Reference: 9
Cont….
• Metatungstate:
When the solution is highly acidic, it is possible to crystallized from the
solution to form a second Dodecatungstate , which is also known as
Metatungstate. An example of Metatungstate is K6[H2W12O40]. 18H2O. This can be
prepared by boiling the solution of normal tungstate with tungstic acid. In this
structure is also WO6 octahedral. And the arrangement of octahedron is more
symmetrical, so that there is a cavity in the Centre of the ion.
Reference: 10
Cont….
 If the PH of the solution containing [WO4] is adjusted to one, then tungsten
oxide (WO3) is precipitated.
 The relation between various stable species are followed as:
Reference:
11
Cont….
3. Isopoly Vanadates:
Earlier it was known that existed vanadates are of alkali metals and of silver
with ratio R2O: V2O5= 3:1, 2:1 or 1:1. a solution of sodium vanadates are
colorless. Is acid is add to the solution it changes to brown red color which
immediately change into yellow orange color Metavanadate is obtained, which
in solution. Form is either Trimer [V3O9] OR Tetramer [V4O12].
Reference: 12
Unstable Intermediate Formation:

VO43- + H+ [VO3(OH)]2
2[VO3(OH)]2 [V2O6(OH)]3- + H2O
[VO3(OH)]2 + H+ [VO2(OH)2]
3[VO3(OH)]2- + 3H+ V3O93- + 3H2O
4[VO3(OH)]2- + 4H+ V4O124- + 4H2O
Reference: 13
Cont….
Decavanadate is formed at PH 6. this ion, then gets protonated in turn to
[H2V10O28]. However when the PH is reduced to 2, then [VO2] ions are
formed which are hydrated and V2O6 are separated out. When various
efforts were employes to isolate vanadates from solutions containing
Isopoly vanadates at various PH. But the stoichiometries did not give
information about nature of species in solution.
Reference: 14
Cont….
4. Isopoly Anions of Niobium and Tantalum:
Niobate and tantalate Isopoly anions can be obtained by fusing the

oxides in excess of alkali hydroxide or carbonate by dissolving metal
into water. The precipitation of niobium occur at PH 7. And
precipitation of tantalate occur at PH 10.
Reference: 15
Cont….
Example of Niobium:
Reference: 16
Cont….
Example of Tantalate [TA6O19]:
Reference: 17
Structure of Isopoly Acids
• There is some improvement is done on the structures of Isopoly

molybdates and Isopoly tungstate. In these both types, three occurs the
union of MoO6 or WO6 octahedra.
• For example, [Mo7O24] anion in ammonium para-molybdate possesses
similar structure.
Reference: 18
Structure of Isopoly Acids
Cont….
 The structure of [V10O28] in two decavanadates Ca3V10O28. 16H2O.

And K2Zn2V10O28. 16H2O has been determined by X-ray studies.
The structure of this anion consist of ten VO6 octahedra which are
joined by sharing their edges. The structure of V10O28 as:
Reference: 19
2. Heteropoly Acids
Introduction:
 These acids are obtained by union of varying number of
acids anhydride molecules .
 It generally involves WO3, MoO3 and V2O5
 It combine with other acids which could furnish the
central atom of whole complex anion.
 The ability to act as a central atom in heteropoly acids is
found amongst acids forming elements as well as among
the metals of the transition seies.
Reference: 20
Cont….
 Heteropoly acids are extremely soluble in polar solvents such as
water, lower alcohols, ethers, esters, ketones, etc.
 Heteropoly acids and their salts may be formed by coordination of
the central atom with four to six oxo anions, which may be
mononuclear (containing one metal ion each), as in H7[P(MoO4)6], or
trinuclear (containing three metal ions each), as in H3[P(W3O10)4].
 Incomplete replacement of oxygen atoms in PO43− ions by
MoO3 groups can result in dimers (two-molecule polymers), as, for
example, {OP[O(MoO3)3]3}26−
Reference:
Structure of Heteropoly Acids
 Heteropoly acids are condensed products which

consist of inorganic oxyacids of phosphorus,
silicon, etc. and that of tungsten, Molybdeum
and Vanadium, etc.
 The hetero atom is present at the centre.
Fig 1.1. Structure of Polyacids
Reference: 22
Preparation of Heteropoly Acids
 These acids are obtained by union of varying number of acids

anhydride molecules .
 It generally involves WO3, MoO3 and V2O5
 It combine with other acids which could furnish the central atom
of whole complex anion.
 Salts of polyacids are obtained by acidifying this solution to an
appropriate hydrogen ion concentration.
 Different ratios of acid anhydride molecule and acid are taken.
Reference: 23
Cont….
 These are extracted from aquous solution by ethers and

esters.
 Purification is done by performing crystallization from water
or organic solvents.
 Preparation of heteropolyacids belonging to unsaturated
series is very difficult.
 These compounds ate obtained by the decomposition of co
ordinate compounds by hydrolytic reaction with OH- ions.
Reference: 24
Properties of Heteropoly Acids
1. These heteropoly acids are soluble in ethers and water. Small metal ions
are soluble in water while large metal ions are not. E.g. Pb+, Ba=2 and
Cs+3 are insoluble in water.
2. These are attacked by hydroxyl ions and completely decomposed by
strong alkali.
34OH+[P2Mo18O62]-6 18MoO4-2+16H2O
3. Heteropoly acids exhibit isomorphism. In these compounds the
coordinate radicals Mo2O7 could replace W2O7 or vice versa
without bringing any change in crystalline form
H8[Si(Mo2O7)6] H8[Si(W2O7)6]
Reference: 25
Cont….
4. It exhibit very high basicity but the maximum permitted

basicity is never reached.
5. These acids form insoluble precipitates with many
complexe organic compounds such as Albumin and
various alkaloids.
Reference: 26
Types of Heteropolyacids
 1 (Tetrahedral heteroatom)
 2 (Octahedral heteroatom)
Reference:
27
1. Tetrahedral Heteroatom
In these the heteroatoms are tetrahedrally coordinated and smaller hetero atoms like
phosphorous and silicon are in series A heteropoly acid. Total 12 octahedron units
arranged in 4-groups around the central heteroatoms. Each group have further three
octahedra around the heteroatom.Actually a tetrahedral cavity is formed between the
12-parental atoms. And heteroatom actually present in cavity which formed by the
parental atom.
Reference:
28
Cont…. (structure):12-Molybdic phosphate
Examples:
[PMo12O40]-3
[PW12O40]-3
Oxygen-atoms
Heteroatom-
phosphorous
Mo,W
octahedron
Reference:
2. Octahedral Heteroatom
In series B the large size heteroatoms will be present in between the parental
atom. Th+4 ,Ce+4,Sn+4 like large size hero atoms are present in between the
cavity. In such heteropoly acids the hetero atom is tetrahedrally coordinated and
hence similar to 1:12 heteropoly acids.
Prepare by keeping 1:12 heteropoly acid acidic medium means at low PH 1-2.
While 2:17 is obtained by partial hydrolysis at controlled PH of solution. Some time
due to substitution reactions 2:18 change into 2:17 then change into molybdic acid
or tungstic acid and this will consume some extra base(more alkali).
Reference: 30
Cont….
Structure # 2:18
heteroatom
heteroatom 31
Oxygen atom octahedron 2
Metal Clusters
• Metal-metal bond is a bond between two transition metal

centers, particularly which ranges from a single to a quadruple
bond.
• The transition metals can form three general types of bonds
such as Covalent bonds, Dative bonds and Weak metal-
metal symmetry interactions where covalent bonds being the
strongest and symmetry interactions are the weakest.
• The compounds containing a large number of metal-metal
bonds forming triangular and larger structures are called cluster
compounds, however these also include linear M-M bonds.
Reference:
http://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/chemistry 32
Metal Clusters
 The molecular complexes containing metal-metal bonds that form

triangular or larger structures are called as metal clusters, however the
linear metal-metal bonds also come under the category of metal clusters.
Therefore, any metal complex having a bond between two metal ions is
called a metal cluster.
 Most of these cluster compounds are homo-metallic; however there are
few exceptions with hetero-metallic cluster complexes.
Reference: 33
http://epgp.inflibnet.ac.in/epgpdata/uploads/epgp_content/chemistry
General methods of preparation of metal cluster compounds
1. By pyrolysis of metal carbonyl complexes:

This method is mainly applied to metal carbonyls where the lower carbonyl
complexes are heated to expel few but not all carbon monoxide molecules. The
unsaturated fragments thus formed can rearrange and react to form higher metal
carbonyl complexes containing metal-metal bonds.
Ru(CO)5 Ru3(CO)12
2. By nucleophilic attack of a metal carbonyl anion:

A metal carbonyl anion can show a nucleophilic substitution reaction with
bromopentacarbonylrhenium(I) which possesses a replaceable bromide.
The reaction results in the formation of a Mn-Re covalent bond.
Reference:
Mn(CO)5- + BrRe(CO)5 (CO)5Mn-Re(CO)5
3. Binuclear reductive elimination:
Reductive elimination takes place at metal centers with higher oxidation states where the oxidation state of
the metal ion undergoing reaction is reduced by two units in the product.
HMn(CO)5 + MeAuL (CO)5Mn-AuL + MeH

4. By the addition of metal to a metal-metal multiple bond.
This method was developed by Green and coworkers and was based on
the isolobal analogy between the M=M multiple bond and an alkene.
Reference:
5. By using bridging ligand.
Few chelating ligands such as common diphosphines (Ph2PCH2PPh2)
has the ability to either act as a chelating ligand to bind one metal ion or to
act as bidentate ligand to coordinate with two metal ions.
Reference:
36
Reactions of metal cluster compounds
• Reaction with Electrophile:
The proton (H+) can be considered as the simplest electrophile
because it is a zero- electron species and smallest in size.
Therefore, it can undergo addition reactions with a variety of
compounds with great ease.
Reference:
Bulkier electrophiles, on the other, are hesitant to act as bridging
species and often display reactions at carbonyl ligands in a reaction
with metal carbonyl cluster
 Reactions with nucleophiles:

Addition of nucleophiles adds two electrons to the metal cluster. Addition of two
electrons to the metal cluster must either rearrange or loose a two electron ligand.
Reference:
 Oxidative addition:
Oxidative addition is the reaction that adds two electrons to the cluster on reaction.
In carbonyl clusters, the loss of one carbonyl is required to keep the cluster
structure intact. Oxidative addition reactions take place with different mechanisms
with different ligands.
Reference:
39
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Presentation Topic

Poly Acids & Metal Cluster

Mr. Khalil Butt

Naila Sehar Maryaam Tariq Nouman tariq

Zeeshan Ashraf Nouman tariq Amara Aslam

3 Types of Iso polyacid 6

6 Structure, Preparation and 22

There are two types of poly acids.

Isopoly acids are inorganic acidic compounds that form from

Unstable Intermediate Formation:

Niobate and tantalate Isopoly anions can be obtained by fusing the

• There is some improvement is done on the structures of Isopoly

 The structure of [V10O28] in two decavanadates Ca3V10O28. 16H2O.

 Heteropoly acids are condensed products which

Fig 1.1. Structure of Polyacids

 These acids are obtained by union of varying number of acids

 These are extracted from aquous solution by ethers and

4. It exhibit very high basicity but the maximum permitted

Cont…. (structure):12-Molybdic phosphate

• Metal-metal bond is a bond between two transition metal

 The molecular complexes containing metal-metal bonds that form

1. By pyrolysis of metal carbonyl complexes:

2. By nucleophilic attack of a metal carbonyl anion:

Mn(CO)5- + BrRe(CO)5 (CO)5Mn-Re(CO)5

3. Binuclear reductive elimination:

HMn(CO)5 + MeAuL (CO)5Mn­­-AuL + MeH

 Reactions with nucleophiles:

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HMn(CO)5 + MeAuL (CO)5Mn-AuL + MeH