INORGANIC POLYMER

CHM-2012 (DC)
UNIT-II
Content:

1. Polyacid and Polyanion

2. Isopolychromate

3. Isopolyvandates

4. Hetropolyacids and Heteropolyanions

5. Keggin Structure

6. Reactions of heteropolyanions and isopolyanions

1. Polyacid and Polyanion

 The acids which are obtained as a result of the apparent condensation of number of simple
oxygen containing acid molecule to give compounds containing more than a single
molecule of acid anhydride is called as Polyacid.

 The ions of the polyacids are similarly derived from those of the simple acids by
elimination of O2- ions are known as Polyanions.

 A familiar example is, the reaction of chromate solution(CrO42- which is yellow, with
excess acid to form dichromate (Cr2O72-) which is orange in color.

 Divided into two groups:

(a) Isopolyacids and anions- Acids/anions condense together are of same type.
e.g. MoO6, WO6

(b) Heterpolyacids and anions- Two or more different types of acids/anions condense
together. e.g. Molybdate with phosphate etc.
2. Isopolychromate
 The oxide of chromium (CrO3) is strongly acidic and dissolving in aqueous NaOH forming
discrete tetrahedral chromate (CrO42-).

 The basic unit is isopolychromate is CrO4 tetrahedra.

 Stable at high pH (as the pH is lowered on acidification protonation and dimerisation takes
place. On gradually decreasing the pH of solution the ions such as Cr2O72-, Cr3O102-,and
Cr4O132- are formed by corner sharing of tetrahedral CrO42- units.

 The structure of CrO3 consist of infinite number of linear chains of CrO42- tetrahedra.
Thus, Cr2O72- are formed by the two tetrahedral CrO3 units by sharing O atom as the corner.

 Polymerization does not normally go beyond (Cr4O132-).

 Polyanions are formed by corner sharing CrO42- tetrahedra. The tendency to form large
number of polyacids is linked. The small size of Cr6+ evidently limits it to the tetrahedral
rather than octahedral coordination with oxygen. CrO4 tetrahedral links only through corners
and simultaneously favoring the Cr=O double bonds and so inhibiting the sharing of the
attached oxygen (not with edges). Because edge sharing result in too close approach of the
metal which is destabilizing the small Chromium ion.

Reference Book: Puri ,Sharma and Kalia

Page:1040
3. Isopolyvandates

 When V2O5 is dissolved in strong alkaline solution, monovandate ion, VO43- (also called
as orthovandate) is predominantly formed.

 As the pH is reduced from 13 to 8 (gradual acidification),conduction of monovandate ion

to pyrovandate (V2O74-) or metavandate ion ([VO3]n n-)

 In the solid metavandate, the anion consists of chains of VO4 tetrahedra linked by sharing
corners and the species in solution is almost a trimer, [V3O9]3- or tetramer, [V4O12]4-.

 The metavandate ions do not involve the discrete VO43- ion. The anhydrous metavandate
such as NH4VO3 contains infinite chains of cross-linked VO4 tetrahedra.

 The structure of pyrovandate ion contains two VO43- terahedra.

 All ortho-, pyro- and meta-vandate attains the coordination Number of 4.

 Further acidification of vandate solution, after the neutralization, produces [V 10O28]6-.The
structure is made up of 10 edge sharing VO6 octahedra in which vanadium acquires a
coordination number of 6.

 When [n-Bu4N]3 [H3V10O28] is dissolved in acetonitrile, the tetrabutylammonium salt of

[V5O14]3- anion is formed . The anion is first example of the transition metal polyoxyanion
which has a cage structure that is built entirely from corner shared MO4 tetrahedra instead
of edge shared or corner shared MO6 octahedra..

Reference Book: Puri ,Sharma and Kalia

Page:1048
4. Hetropolyacids and Heteropolyanions
 The first heteropolyanions, [PMo12O40]3- was reported by J.J. Berzelius which is used now
for the quantitative estimation of PO43- in its solution.

 Heteropolyanions are used extensively as catalyst in petrochemical industry, as precipitants

for dyes with which they form lakes and as a flame retardants.

 The heteroatom in heteropolyanions are situated inside the cavities formed by MO 6

octahedra (M = Mo, W) and are bonded to oxygen atoms of MO 6 units of condensing
MO6 octahedra.

•It can be prepared by-

Five Important categories of heteropolyanions are-

(a) 1:12 (tetrahedral Heteroatom) Polyanion:

• The heteroatom here is relatively small in size and is situated in a tetrahedral inner cavity of
the polyanion, i.e. heteroatom is tetrahedrally surrounded by four O atoms inside the
polyanion.

• Common heteroatom's are P, As, Ti, Ge, etc.

• The structure of this category has either full tetrahedral symmetry (Td) (keggin structure) or
has a structure which can be derived from Keggin structure by rotating one of the four sets
of the three condensed MO6 octahedra of Keggin structure by 60o

https://en.wikipedia.org/wiki/Keggin_structure
(b) 2:18 (Tetrahedral Heteroatom) Polyanion

• The general formula is [X25+M18O62]6- , M = Mo, W; X = P, As.

• The structure of this polyanion is called “Dawson structure”.

• If the three corner linked MO6 octahedra are removed from the keggin structure to leave a
structure with a set of three octahedra over a ring of six octahedra, one half of [X25+M18O62]6-
anion is produced. If two such halves are fused together by sharing corner of their MO6
octahedra, Dawson structure results.

https://www.google.com/search?q=P2W18O62%5D6-
+structure&rlz=1C1ASVA_enIN860IN860&source=lnms&tbm=isch&
sa=X&ved=2ahUKEwjZ_sntqbXoAhVCfX0KHdNqDMAQ_AUoAXo
ECAsQAw&biw=1024&bih=657#imgrc=sCnVFDWP1GqF2M
(c) 1:6 (Octahedral Heteroatom) Polyanion

• Formed by large sized heteroatoms like Te, I, Co, Al, etc.

• These heteroatoms are octahedrally coordinated to six oxygens of six edge sharing MO 6
octahedra. e.g. [Xn+M6O24](12-n)-

Reference Book: Puri & Sharma

Page:1051
(d) 1:9 (Octahedra Heteroatom) Polyanion

• General Formula: [Xn+Mo9O32](10-n)-

• These heteroatoms are octahedrally coordinated to six oxygens of six edge sharing MoO6
octahedra. e.g. [NiMo9O32]6- and [MnMo9O32]6- with Ni and Mn in unusual oxidation
state of +4.

Reference Book: Puri & Sharma

Page:1051
(e) 1:12 (Icosahedral Heteroatom) Polyanion

• General formula: : [Xn+M12O42](12-n)-

• Contain the heteroatom Ce, Th, or U which are icosahedrally surrounded by 12 oxygen
atoms of MO6 octahedra.

Reference Book: Puri & Sharma

Page:1051
5. Keggin Structure (Polyoxometalate-POM)

 Keggin structure is the best known structural form of Heteropolyacids.

 α-Keggin anions have the general formula [XM12O40]4-, where, X=heteroatom (most
common P3+, Si4+, Bi3+ ), M = Mo, W and O = Oxygen.

 The first α-Keggin anion, ammonium phosphomolybdate, (NH4)3[PMo12O40], was first

reported by Berzelius in 1826.

 But J.F. Keggin could only characterize them structurally in 1933. He solved the structure
of the free acid, H3PW12O40 using powder x-ray diffraction.
 The structure is composed of one heteroatom surrounded by four oxygen atoms to form a
tetrahedron. The heteroatom is located centrally and caged by octahedral MO6 units
linked to one another by the neighboring oxygen atoms. There are total of 24 bridging
oxygen atoms that link the 12 addenda M atoms. The metal centers in 12octahedra are
arranged on a sphere almost equidistant from each other, in four M13O13 units, giving the
complete structure, an overall tetrahedral symmetry.

 The bond length between atoms varies depending on the heteroatoms (X) and the addenda
metal atoms (M). For the 12-phosphotungstic acid, Keggin determined the bond length
between the heteroatom and each of the
4 central O atoms to be 1.5Å.

 The bond length between the addenda atoms and

each of the bridging O is 1.9 Å.

https://en.wikipedia.org/wiki/Keggin_structure
 The remaining 12 O atoms that are each double bonded to addenda atoms have a bond
length of 1.7 Å. The Octahedra, therefore, distorted. This structure allows the molecule to
hydrate and dehydrate without significant structural changes and the molecule is thermally
Stable in the solid state.

 Including the original α-Keggin structure, there are 5 –isomers, designated by α, β, γ, δ

and ε.

 These isomers are sometime termed as Baker, Baker-Figgis or rotational isomers.

 In general, α-Keggin anions are synthesized in acidic solutions. For example, 12-phospho-
tungstic acid is formed by condensing phosphate ion with tungstate ion.

 α-Keggin have been used a catalyst in hydration, polymerization and oxidation reactions.
For example, in hydration of propene, oxidation of methacrolein, etc.
 6. Reactions of heteropolyanions and isopolyanions
1. Reactions with isocyanides:

Isocyanides react with heteropolyanions to convert a terminal M=O to M=NR.

For example, [Mo6O19]2- and [W6O19]2- react with RNCO to yield products like
[W6O18NAr]2-,Mo6O17(NPh)2]2-, [Mo6O15(NAr)4]2-etc.

2. Reduction:

 The reduction of isopoly and heteropoly molybdates and tungstates yield blue species
(heteroblue species formation).

 The reductions are reversible and structural features of the species are retained
during reduction.

.
 The added electro is weakly localised on one Mo atom but it gets delocalised on all the Mo
atoms when Mo6O19]3- is subject to heat.

 The reduction of Keggin ion, [PW12O40]3- yields [PW12O40]7-. The 4 added electrons in
the product appear to be distributed in such a way that each subunit, having three edge
shared WO6 octahedra, of the structure has one added electron.

 The Dawson ion [X2Mo18O62]6- (X= P,As) can also be reduced reversibly to yield blue
species.

 The transfer of electrons from the reduction of heteropolyanion is reversible for the
intense charge transfer absorption in the visible region and hence for the deep color
shown by these ions.