UNIVERSITY OF NAIROBI

CAMPUS CHIROMO
COLLEGE BIOLOGICAL AND PHYSICAL SCIENCES
SCHOOL PHYSICAL SCIENCES
DEPARTMENT CHEMISTRY
UNIT CODE SCI 504
UNIT TITLE ADVANCED POLYMER CHEMISTRY AND TECHNOLOGY

TASK TERM PAPER

LECTURER PROF ONYARI

STUDENT DETAILS REG NO

NAME MUTHANGA MAWIRA ARNOLD 156/8251/2017
DATE 27/11/2017

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 Inorganic and Organometallic Polymers and their Applications
1.0.0 Abstract ................................................................................................................................................ 3
1.1.1 Introduction ......................................................................................................................................... 3
2.0 Methodology....................................................................................................................................... 4
3.0.0 Results and discussion ................................................................................................................. 4
3.1.1 Pure inorganic polymers .............................................................................................................. 4
3.1.2.Inorganic-organic Polymers ......................................................................................................... 4
3.2.0 Inorganic Polymers; A Review of Synthetic Strategies ................................................................ 4
3.2.1 Unsaturated inorganic compounds ............................................................................................. 4
3.2.3 Inorganic Polymers from Acyclic Monomers ............................................................................... 5
3.2.4 Polymer synthesis from two monomers ...................................................................................... 9
3.2.5 Ring Opening Polymerization of Cyclic Inorganic Compounds .................................................. 12
3.3.0 Properties of Inorganic Polymers............................................................................................... 16
3.3.1 Applications of Inorganic polymers ........................................................................................... 17
4.0.0 Organometallics Polymers ..................................................................................................... 17
4.1.1 Polystannanes ........................................................................................................................ 18
4.1.2 Synthesis of Polystannanes .................................................................................................... 18
4.2.0 Ferrocene Polymers ............................................................................................................... 20
4.2.1 Synthetic Strategies ............................................................................................................... 20
4.2.2 Properties of Organometallic Polymers ................................................................................. 22
4.2.3 Applications of Organometallic Polymers .............................................................................. 22
5.0.0 Conclusion .......................................................................................................................... 23
6.0.0 References ......................................................................................................................................... 24

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1.0.0 Abstract
Inorganic polymers contain inorganic elements as part of their backbone or as a side group. They
have a variety of combinations offering a wide range of unique properties and novel applications.
They can be roughly classified into pure inorganic, inorganic-organic, organometallic and hybrid
organic-inorganic networks. Organometallic compounds have at least a carbon either to the metal
bond that can be a direct carbon bond (sigma bond) or as a metal complex (pi-bond and lone
pair). The nature and character of the metal carbon bond exhibits ionic, covalent or in between
properties that determine their chemical properties. Organometallic complexes have a dative
covalent bond between the metal and organic ligands. The review has focused on the various
methods of synthesizing both inorganic and organometallic polymers, their physical and
chemical properties. It concludes with a brief focus on their applications in modern day
industries. The polymers considered in these two families are few examples of the broad topic of
each class. Polymers with high commercial value have been considered.

1.1.1 Introduction
The type of materials used by man is a good indicator of human civilization progress. Polymeric
materials that have better properties are quickly substituting conventional materials such as iron,
glass, wood, and steel. They are attracting attention as high technology materials, biomedical
polymers, and electrical conductors. Ability of carbon to form bonds to itself and other
heteroatoms has allowed the synthesis of a wide variety of different polymers. Availability of an
inexpensive petroleum feed stock has given rise to large-scale presence of polymer building
blocks essential for synthesis of polymeric materials.
However, carbon based polymeric materials that constitute organic polymers have some
limitations. First, they are brittle at low temperatures and are oxidatively degraded at high
temperatures. Organic polymers have good flammability properties requiring fire retardant
additives making them fall short of meeting the current market demands. Organic polymers react
with oxygen or ozone over long duration, losing their advantageous properties. Secondly,
petroleum stocks are quickly being exhausted regardless of the coal deposits that can be used as
substituents. Material scientists have opted for polymers with inorganic elements to supplement
the conventional systems.
Inorganic macromolecules have unique property profiles due to their bond angles and bond
torsional mobility. There are a number and variety of elements composed of these polymers, high
abundance of inorganic elements in the earth’s crust, strong and long bonds that are resistant to
cleavage reactions, different valancies for side group attachment, stability at high temperatures
and possible modifications into new structures than carbon. The unique trend has prompted an
infinite area of material scientist exploration.
It is important to note, pure inorganic polymers are still few, and in several accounts inorganic
polymers have organic groups as side groups and in the backbone. They co-exist and are
discussed as such in this paper.

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2.0 Methodology
Studies were identified by online database searches and hard searched in the library. Eligible
studies both published and unpublished were considered in the review. Among the five papers
used, there were few variability of terms. In some notable studies, there was a contradiction in
the definition of inorganic polymer in reference to the inorganic group. There is a wide range of
materials on inorganic and organometallic polymers. The analyses of these studies and there
implications are discussed.
Keywords: inorganic polymers; organometallic polymers

3.0.0 Results and discussion

3.1.1 Pure inorganic polymers
They largely constitute the mountains, soil, and sand. They are employed as abrasives and
cutting materials-diamond, fibers-asbestos-fibrous glass, coatings, flame-retardants, lubricants
and catalysts- zinc oxide-carbon black, building and construction materials-window glass, stone,
cement. The commonly used of these polymers include Portland cement, polymeric carbon,
silicon dioxide and poly sulphuric nitride.

3.1.2.Inorganic-organic Polymers
These inorganic polymers contain portions of inorganic elements in their main chain such as
polysilanes, polysiloxanes, polyphosphazenes. Other type of polymers have inorganic elements
as pendant groups, they include polystyrene. These polymers in their cross-linked form they
interact with transition metals to form heterogeneous metal carrying polymers that are good
catalysts for organic reactions. The above methodology has been used to anchor inorganic motifs
as pendant groups. N3P3Cl5-OCH=CH2 cyclophosphazene undergoes free radical polymerization
to constitute a high molecular weight polymer with heterocyclic ring inorganic groups as pendant
groups.
It can be used in preparation of polymers with organometallic side groups. Ferrocenylethylene is
polymerized to obtain polymers with ferrocene pendant groups. Standard organic polymerization
methods have been used in preparing piano-stool polymers with organometallic complexes as
side groups. More so hybrid organic inorganic networks are multi-functional materials prepared
through sol-gel process.

3.2.0 Inorganic Polymers; A Review of Synthetic Strategies

Inorganic compounds like inorganic oxides or inorganic nitrides are built from the basic
structural groups. Inorganic polymer synthesis addresses the aspect of covalent bond formation
between similar and dissimilar inorganic elements to form polymeric structures (Chandrasekhar,
2004).

3.2.1 Unsaturated inorganic compounds

These are inorganic compounds that contain double or triple bonds between them e.g.
H2Si=SiH2. Silicone analogues of alkane are extremely reactive and burn spontaneously in air,
an observable presumed to be characteristic with corresponding analogues of ethylene and
olefins.

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 Initially, double bond role, argued it wasn’t possible to form main group elements with double
bond between them. The assumption was based on the large size consequently long inter-atomic
distances –relative to carbon- of heavier main group elements. An additional p-orbital overlap
among heavier main group elements would result to such a weak double bond. Utilization of
sterically hindered groups for stabilizing these reactive compounds kinetically led to the isolation
and characterization of main group containing double bonds. Large sized substituents were used
to sterically protect the resultant double bonds. Si=Si, P=As,Bi=Bi stable compounds were
synthesized and characterized (Jamshidi & Rahimi, 2007). As the size of the main group element
increases there is an increase in sterically hindered group. The stabilization method limits the use
of these monomers for polymer synthesis. In situ formed disilene iPr2=SiiPr2 undergoes
spontaneous oligomerization to form cyclic tetramer iPr2Si4
Olefins are reactive however their reactivity can be suitably directed to generate products with
inclusion of polymers. Polymerization of unsaturated inorganic products remains a synthetic
obstacle. (MesP=CPh) 2 can be polymerized to polymers with moderate molecular weight by
radical or ionic initiators.( MesPCPh2)n

3.2.3 Inorganic Polymers from Acyclic Monomers

Inorganic acyclic monomers have been used in the synthesis of polymers with either inorganic
elements or as inorganic groups. Synthesis route may be
i. Elimination of small molecule from one monomer to obtain a polymer
There are various reactios used to obtain polymers from single monomer. Dehydration of
diorganosilane diols generate organosiloxanes. Similarly, dimethyldichlorosilane is hydrolysed
to obtain [Me2Si(OH)]2 that undergoes self-condensation to obtain poly(dimethylsiloxane) with
elimination of water forming (Me2SiO)n (Chandrasekhar, 2004).

Hydrolysis of PhSiCl3 yields PhSiOH3 that undergoes self condensation to form ladder type
polysilsequioxane.

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Polysilanes with catenated organosilicon units are prepared using metal assisted reaction akin to
the Wurtz reaction. Diorganodichlorosilanes react with fine sodium in boiling solvent like
toluene to achieve polysilanes. Sodium chloride is eliminated in the process. Molecular weight of
such polymers varies from low to moderate. Phynlmethylchlorosilane reacts with sodium to form
poly(methylphenylsilane). An approach used to prepare poly-dialkylsilane and poly(diarysilanes)
also polysilanes with mixed substituents.

Wurtz coupling reaction is not favourable for reactive groups such as halogens and hydroxyl
groups. Wurt-coupling has been used to prepare various polysilanes copolymers.
Phenylmethyldichlorosilane and dimethyldichlorosilane react with molten sodium in boiling
toluene to form PhMeSi Me2Si copolymer units of high molecular weight. Polysilanes have a
sigma conjugation in their main chain. They are being investigated for electronic applications.
Polysilanes are sensitive to light, undergoing photoscission on light exposure. The property is
more conspicuous in solution state then solid state. Photo bleaching has attracted their use in
photoresists in microlithography.

Polymers with Si-Si sigma bonds conjugated with organic pi structures are prepared through
dehalogenation. Dichlorosiloles react with lithium metal to form 1,1(polysiloles).

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High molecular weight polystannane is prepared via dehalogenation (Chandrasekhar, 2004). Poly
(dialkylgermanes) is also prepared through Wurtz coupling reaction.

Alternatively, polysilanes are prepared through catalytic dehydrogenation. It involves

dehydrogenation of RSiH3 to form (RSiH)n type polysilanes.

Several complexes of titanium or zirconium organometallic complexes catalyze

dehydrogenation processes. Molecular weight of polysilanes obtained through dehydrogenation
is usually lower than those prepared through Wurtz-type dehalogenation. Dehydrogenation is
limited to arylsilanes with alkyl silanes unreactive to the reaction with exception of CH3SiH3.
Polymers prepared through dehydrogenation have a reactive Si-H group that can be used for
further hydrosilylation reactions. This method cannot be used to prepare polysilanes of the type
(RRSi) n.
Polystannanes can be prepared using catalytic dehydrogenation obtaining even R2Snn type.
Dialkyltindihydrides R2SnH2 are dehydrogenized by zirconocene catalysts to form high
molecular polystannates H-SnR2-H with a reactive Sn-H groups (Chandrasekhar, 2004).

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Hydrogen is lost by heating inorganic heterocyclic ring B3N3H6 to obtain interconnected
borazine rings, useful precursors for preparing ceramic boron nitride.

Thermal treatment of PhPH2.BH3 with 1, 5(COD (Rh)Cl) gives PhHPBH2 a linear polymer
poly(phenylphosphinoborane).

Condensation polymerization among many other synthetic routes can be used to prepare
polyphosphazenes with phosphorous and nitrogen atoms alternating in the main chain. On
heating monophosphazene precursors like Me3SiNPRR’ROR’’ known as N-silylphosphoranimes
with the elimination of silyether Me3SiOR they form polymeric materials. Poly-
alkyl/arylphosphazenes are prepared this way. To get poly (dimethylphosphazene) N-
silylphosphoranimine Me3SiN=PMe2 (OCH2CF) 3. is heated (Jamshidi & Rahimi, 2007).

Poly (oxothiazene) with alternating nitrogen and sulfur atoms in the main chain is prepared in the
same strategy. High polymers are formed by the elimination of silylethers from Me3SiN=S (O) R
(OR) or phenols.

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Poly (dichlorophosphazene) is prepared from acyclic monomers. On heating acyclic
phosphazene derivative Cl3P=N-O-Cl2 P-O-Cl3 is eliminated leading to the formation of linear
polymer polydichlorophosphazene (NPCL2) n

Alternatively polydichlorophosphazene are prepared by reacting Cl3P=NSiMe3 with PCl5,

generating high molecular weight living polymer.

Anionic polymerization is used to prepare polyphosphazenes from acyclic monomers.

Me3SiNP(OCH2CF3)3 reacts with Bu4NF to form –NP(OCH2CF3)n

3.2.4 Polymer synthesis from two monomers

It involves coming up with di-functional inorganic monomer that react with each other to form
linear polymers. Inorganic compounds with di-functional compounds such as diols, diamnines
and dicarboxylic acids are rare due to their high reactivity that need controlled polymerization
process. Si-OH and SiNR2 do exists and have been used in condensation polymerization. R2NH
group is eliminated during polymerization process to form Si-O-Si bond.

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When diphenylsilanediol undergoes condensation polymerization, it forms polysiloxane
copolymer of alternating Me2SiO and Ph2SiO units. Si-N bonds cleavage to form thermal stable
Si-O with the eli

mination of insoluble by-product of urea that act as a driving force for the reaction.

Poly(1,1’siloles) are prepared by dehalogenation of silole dichlorides unlike the multistep

procedure for poly(2,5-silole-s). 2,5(diiodosilole) is selectively converted to monozinc derivate
that cross couples with palladium mediator forming poly(2,5-silole) with moderate DP.
A mixture of E/Z poly-p-phenylene phosphaalkene is formed via condensation polymerization of
silylated phosphane (Me3Si-2P-C6H4-p-P-SiMe3)2 with a diacid chloride.
Condensation polymerizations are used in the formation of poly(1,1-ferrocenylenes) with
ferrocene units within the chain. 1,1 –dilithioferrocene reacts with 1,1- diiodoferrocene to obtain
a moderate molecular weight polymer. The condensation of alkylferrocenyldialdehydes is
catalyzed by Zn/TiCl4 to form poly(ferrocenylvinylenes). They are organometallics with linearly
conjugated organic polymers like poly(1,4-phenylenevinylene).

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Rigid-rod architecture of organometallic polymers have been prepared using condesation
synthesis of trans(Pt-PnBu3-2-CCCCH)2 with trans(Pt-PnBu3)2Cl)2. The reaction is catalyzed by
Cu(I) salts and carried out in amine solvents. The monomer is synthesized by reacting trans (Pt-
II-Cl2-nBu3P)2 with 1,3-butadiyne to form alkynylated trans (Pt-PnBu3-2-CCCCH)2 that has M-C
sigma bond. The obtained metal derivative can be coupled with Pt-II-Cl2nBu3P2 to obtain a high
molecular weight polymer. The rod-like structure is due to the rigidity imposed by the akylnyl
groups. They are characterized by metal to alkyne charge transfer transitions. The synthetic route
has been widely used in preparation of rod-rigid polymers that contain transition metals such as
ruthenium, cobalt, nickel. They have nonlinear optical properties making them of interest.

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Condensation polymerizations, as a synthetic route for inorganic polymers, always call for highly
pure monomers to obtain high molecular weight polymers.

3.2.5 Ring Opening Polymerization of Cyclic Inorganic Compounds

Heating S8 at 160 degrees makes it to undergo ROP to form an elastomeric linear polymeric
sulphur (S)n polymerization of rhombic sulphur. It is one of the pure inorganic polymers that has
limited use due to depolymerization on cooling to room temperature (Chandrasekhar, 2004).

S4N4 a S-N cages and rings of sulfur when it combines with nitrogen. S4N4 is heated to form
S2N2, which undergoes polymerization to form polythiazyl. (SN) n.

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Polythiazyl is a pure inorganic polymer insoluble in organic polymers with interesting electrical
conductivities. It portrays metal like conductivity at room temperature with superconductivity at
0.3 K.
Inorganic siloxane are polymerized by both cations and anions initiators to afford polymeric
siloxanes. Octamethylcyclotetrasiloxane Me2SiO4 is polymerized to poly (dimethylsiloxane)
(Me2SiO) n by use of KOH initiator. Polysilanes inorganic polymers have a high commercial
demand.

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Cyclic monomer tetrasilane (PhMeSi) 4 is polymerized to (PhMeSi) n with nBuLi as an initiator.
nBuLi initiator is used for polymerizing masked disilenes, which are basically disilane that exist
as trapped or masked disilenes. They can essentially cyclize or polymerize. Carefully selected
masked disilenes have found great use in formulating polysilanes polymers.

Polymers with alternating silicon and carbon centers are known as silylene ethylene or
carbosilanes. They are prepared through polydimethylsilane thermal rearrangement (Me2Si) n.
Recently they are prepared by ring opening polymerization of four membered disilacyclobutanes.
Cyclo(Cl2SiCH2)2 undergo ROP to form poly(dichlorosilaethylene) (Cl2SiCH2)n using H2PtCl6
catalyst. Poly (dichlorosilaethylene) can be reduced to poly (silaethylene) (H2SiCH2) n using
LiAlH4. Poly (silaethylene) is an analogue of polyethylene where SiH2 replaces CH2 groups.

H2PtCl6 is used to catalyze ring-opening polymerization of silacyclobutanes to form

polysilaethylenes, which contain alkyl groups on the silicon.

High molecular weight poly (ferrocenylsilanes) is formed as a result of thermal ROP of cyclic
silicon bridged 1ferrocenophanes. Polymers of these families are possible with the center silicon
replaced by Sn (IV), B (III),

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Ferrocenyl polymers are also prepared by extraction of sulfur from a ferrocene monomer. A
trisulfide unit joins two cyclopentadienyl units. Tertiary phosphine that forms phosphine sulfide
facilitates sulfur elimination leading to ring opening polymerization.

Cyclophosphazenes are inorganic heterocyclic rings with phosphorous and nitrogen atoms
alternation. Poly (dichlorophosphazene) (NPCl2) n is as a result of ROP of
hexachlorocyclophosphazene N3P3Cl6 at 250 degrees. The polymer is hydrolytic and example of
pure inorganic polymer that can be used in the preparation of poly-organophosphazenes like [NP
(OR) 2] n, [NP(NHR)2]n and [NP(NRR’)]n.

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Hydrolytic sensitive poly-carbocyclophosphazene is obtained by thermal treatment of
pentachlorocarbocyclophosphazene N3P2CCl5 with a heteroatom of carbon in place of
phosphorous.
N3P2SCl5, pentachlorothiophosphazene with S (IV) heteroatom are polymerized through ROP to
obtain poly (thiophosphazene).

More so [N3P2S (O) Cl5], is polymerized by thermal ROP of pentachlorothionylphosphazene.

3.3.0 Properties of Inorganic Polymers

Polysilanes, a general term to describe organo-silicon compounds, have silicone atoms in their
backbone and are the most attractive and challenging. They include polysiloxanes, polysilanes,
polysilazanes, and polycarbosilanes. They demonstrate unique properties due to ease of
delocalization of sigma electrons in the Si-Si bonds. Structurally, they may be chains, linear,
rings, or three-dimensional network. Polysilanes solubility and melting points depend on the
molecular weights and nature of the organic groups attached to the silicon atoms. The molecular
weight depends on the method of synthesis. Polysilanes have a range of properties from
crystalline, insoluble, flexible solid, glassy amorphous materials, rubbery elastomers, to
crystalline in less symmetrical structures. Linear polysilanes are thermoplastic, soluble in organic
solvents, and insoluble in alcohols. Tg of soluble polysilanes ranges from 50-120 degrees
depending on the nature of the attached organic groups. They are stable in air and moisture and
are not attacked by dilute acids but Si-Si bond solvylisis in strong basis and in THF. Polysilanes
are stable up to 300 degrees but are degraded on exposure to UV light. They are photoactive with
strong electronic absorption bands and exhibit thermochorism facilitated by the side chain.

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Extensive delocalization of sigma electrons on the main chain that are sensitive to the nature of
the attached pendants greatly contribute to electronic, photo physical, optical and chemical
properties.

3.3.1 Applications of Inorganic polymers

Many of the uses of polysilanes are based on their unusual mobility.
a. Precursors of silicon carbide ceramics
This porous SiC is used to prepare SiC glass composites through the pyrolysis of a mixture of
polysilanes and polycarbosilanes.
b. Protective coatings
Polysilanes are used to prepare the deep-UV (DUV) bottom antireflective coating. The coating is
immiscible with chemically amplified photoresist and not removable during wet development of
photoresist. The layer is easily removed through ashing (Jamshidi & Rahimi, 2007).
c. Photoinitiators in radical reactions
Polysilanes undergo main chain scission on exposure to UV light due to photolysis that involve
hemolytic cleavage of Si-Si bonds to form free silyle radicals.
d. Production of conducting and semiconducting electronic devices
This is possible due to formation of molecular dipoles due to strong charge delocalization of the
pendant respective salt segments
e. Photoconductors in photography and nonlinear optical materials
f. Photoresists in microelectronics
g. High resolution UV resists in microlithography, coupling agents, preparation of nanoporous
thin films, formation of patterns, fabrication of microlens arrays,
New research areas include; substitute for Portland cement, fireproof components for buildings
and vehicles, encapsulation media for storage and disposal of hazardous wastes, removal of
heavy metals from wastewater streams, materials for photo degradation of organic pollutants,
bacteria filter bed for water purification, porous materials for passive cooling of buildings
(Mackenzie, 2011).

4.0.0 Organometallics Polymers

Compounds with atleast one metal to carbon bond, where carbon is a part of organic group R-M.
They are made of over forty elements that include main group metals, transition metals and the
ten-halide elements- C, H, N, O, B, and P found in organic polymers. They combine low density,
structural discrepancies, and functional group varieties of organic materials with electrical
conductivity and high thermal stabilities of inorganic compounds. The metals may be present in
the polymerization product as pendent groups or in the main chain.

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Zeise’s salt K-PtCl3CH2=CH2 was the first organometallic compound to be known. Later
discovery of ferrocene drew great scientific attention to this class of polymers.
The discovery of Ziegler was a major shift in organomettallic polymers. It is organoaluminium
compound that acts as a catalyst in ethylene polymerization and its’ use with titanium halides for
preparation of high-density polyethylene and isotactic polypropylene. Ziegler-Natta catalysts led
to the use of organometallic compounds on industrial scale.
Challenges in finding viable synthetic routes in preparing metal-containing polymers leading to
novel preparative routes, coupled with unusual electrical, magnetic, and optical properties of
these polymers constitute major motivations for scientific interest in this group of compounds.
4.1.1 Polystannanes
Polystannates are heavier Group 14 congeners of polysilanes
Polysilanes have useful properties that are a result of sigma delocalization. Consequently, they
exhibit interesting behavior such as absorption of UV rays in the visible region, semi
conductivity characteristics that are enhanced on doping, thermochromism and
photoconductivity. Polystannates are principally prepared via catalytic dehydrogenation of
diorganotindihydrides.

4.1.2 Synthesis of Polystannanes

Carefully controlled reaction that follows the Wurtz coupling technique of reacting nBu2SnCl2
with sodium dispersion in presence of 15-crown-5-ether in toluene at 60 degrees forms high
molecular weight Bu2Sn-n polymer. An optimum yield is achieved after 4 hours after which
cyclic oligomers such as n(Bu2Sn)5 are formed.

119 Sn NMR is useful in analyzing the constituent polymers and further distinguishing. Wurt
coupling is not a viable synthetic route for preparing polystannanes hence the adoption of a more
successful catalytic dehydrogenation route suitable for R2SnH2 type.
Monomers for the polymerization undergo comproportionation, R4Sn reacting with SnCl4 to
form R2SnCl2 and further reduction by LiAlH4 to form respective dihydrides R2SnH2. The
products are air and temperature sensitive. Several poly-dialkylstannane with fairly high
molecular weights are prepared through catalytic action of organometallic zirconocene catalysts
like Cp2ZrMe2. When an appropriate catalyst is added to the monomer it initiates polymerization
process with the evolution of hydrogen and formation of polymeric material with the presence of
cyclic products. Five membered compounds n(R2Sn)5 are the mostly formed with little amounts
of six membered compounds (R2Sn)6.

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Poly-diarylstannane are synthesized through comproportionation reaction between R4Sn and
SnCl4 yielding R2SnCl2. Followed by a reduction reaction with LiAlH4 to form dihydrides
R2SnH2.

Ar2SnH2 is dehydrogenated using metallocene catalyst to obtain high molecular polymers with
cyclic products mainly hexameric. The separation of the polymeric material and the cyclic
products is achieved through fractionation.

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Polystannanes prepared through the use of zirconocene catalysts are fairly linear contrary to
those prepared through the reaction of nBu2SnH2 with the rhodium (I) catalyst HRh(CO)PPh3]3.
A property explained by the dehydropolymerization rearrangement.
Polystannanes have been synthesized by use of electrochemical methods. N(Bu2Sn)n is prepared
by electrochemical polymerization of dibutyldichlorostannane similar to the preparation of
n(Oct2Sn)n where dioctyldichlorostannane is polymerized. Platinum is used as the cathode and
silver as the anode with a supporting electrolyte of tetrabutylammonium perchlorate and a
dimethyl ethane solvent.
Polystannanes are sensitive to air and moisture especially when in solution form. However, they
exhibit fair thermal stability. They decompose in an atmosphere of flowing nitrogen to tetragonal
tin in bulk pyrolysis. When heated in oxygen, polystannanes form high ceramic residue known as
cassiterite SnO2.

4.2.0 Ferrocene Polymers

Forrocene has drawn scientific interest to incorporate it in polymer framework due to its thermal
and electrochemical robustness.

4.2.1 Synthetic Strategies

Intermolecular linkages of iron centers cannot be carried out due to the eighteen valency of
Ferrocene. In so doing, there would be an increase in the number of ligands exceeding the
number of valence electrons. Bent-metallocenes like CP2TiCl2, Cp2HfCl2, and Cp2ZrCl2 are
considered di-functional monomers that can undergo condensation in presence of other di-
functional reagents such as dicarboxylic acids and diols to form polymers of moderate molecular
weights. To prepare ferrocene polymers, cyclopentadienyl are used as motifs for linkage or
ferrocene groups are used as side chains.
Various synthetic routes that include radical, cationic, or anionic initiators have been used to
obtain poly-vinylferrocene by polymerizing Vinylferrocene. Poly (vinylferrocene) is soluble in
solvents like THF and portrays electronic absorption. It has a single oxidation potential
restraining the interaction of pendant ferrrocene with each other as revealed through
electrochemical studies. Virgin poly (vinylferrocene) is an insulator and its conductivity increase
with doping.

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Poly (ferrocenyl) methyl acrylate and poly-ferrocenyl methyl methacrylate are good examples of
ferrocene pendant containing polymers. They are prepared from free radical polymerization of
analogous ferrocenyl acrylate monomers.

Condensation polymerization has been used to incorporate ferrocenes into the polymer main
chains. It is initiated with a suitable di-functional ferrocenyl monomers. Functional groups are
introduced in the cyclopentadienyl unit without affecting the structure of the ferrocene molecule.
Di-functional reagents 1, 1’dilithioferrocene and 1,1’ -diiodoferrocene reacts with the
elimination of lithium iodide to yield poly(1,1’ ferrocenylene). The synthetic route uses highly
pure starting materials to achieve high molecular weight polymers. It is a daunting condition
when handling highly reactive and sensitive reagents such as 1, 1’-dilithioferrocene.

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Dehalogenation reaction of 1, 1’ dibromoferrocene or 1, 1’-diiodoferrocene using magnesium
has been used to obtain poly (ferrocenylenes). Virgin poly (ferrocenylenes) is insulators, whose
conductivity increases upon oxidation with TCNQ. Other conventional methods of preparing
ferrocene polymers have been used that involve organic functional groups.

4.2.2 Properties of Organometallic Polymers

Organometallic compounds such as organolithium, organomagnesium and organoaluminium are
highly basic and are strong reducing agents. Organometallic compounds may be present in the
environment as organolead and organomercury posting hazardous effects. The common
properties of inorganometallic compounds include, high reactivity, oxidizability, toxicity,
solubility in ether and related solvents, relatively low melting points, and insolubility in water.
4.2.3 Applications of Organometallic Polymers
They act as catalysts or reagents in synthesis of organic compounds, a use based on their high
reactivity and reaction selectivity (Pinkus, 2017). The global production of polyethylene and
polypropylene depends on organometallic catalysts. The polymer achieved is of high density,
high melting point, greater strength and more ordered linear polyethylene. Ziegler-Natta catalyst,
which acts heterogeneously, is used in these reactions.

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Acetic acid is produced through metal carbonyl catalysts used in the Monsanto and Cativa
processes. They are used as Grignard reagents.
Drugs with organometallic fragments, such as metal complexes with platinum center atoms like
cisplatin, carboplatin, and oxaliplatin have demonstrates effective anticancer properties
explaining their use in cancer chemotherapy (Mudi, Usman, & Ibrahim, 2015). Cisplatin is
highly effective in treating ovarian and testicular cancers. Platinum complexes like carboplatin,
exhibit antitumor properties. Cisplatin has fewer side effect. Gold compounds are being used for
treating arthritis, cancer with high possibilities for being used to treat HIV/AIDS, malaria and
Chagas disease. The level of anti-HIV activity in decreasing order of metal complexes is
identified as Zn>Ni>Cu>Co>Pd. In Zinc and vanadium, exert insulin mimetric in in vitro and in
vivo due to presence of organic ligands that have experimentally shown improved glucose
utilization. They have found use as anti-inflammatory agents based on their physical and
chemical properties of the complex itself. They are stable and have been used as pestcides.
5.0.0 Conclusion
Inorganic polymers have high molecular weight polymers with inorganic backbones or as
substituents. Inorganic polymers have a flexible macromolecule, ability to react with chemical
reagents, stable at high temperatures and have favorable interactions with solvents and other
polymeric molecules. Elements with non-carbon backbone provide better chances of tailoring
various molecules that are not possible with organic macromolecules. They have found
application in almost every industry.
Organometallic compounds and complexes have therapeutic potential on curing cancer, diabetes,
HIV/AIDs, malaria and Chagas disease. Several organic compounds such as alcohols, acetic
acids, polyethylene and polypropylene are produced though the catalysis of organometallics. The
review met it objectives.

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6.0.0 References
Chandrasekhar, V. (2004). Inorganic and Organometallic Polymers.

Jamshidi, H., & Rahimi, A. (2007). Applications of Inorganic Polymeric Materials II: Polysilanes.
Phosphorus, Sulfur, and Silicon and the Related Elements, 11(181), 2565-2576.
doi:10.1080/10426500600775765

Mackenzie, K. J. (2011). Inorganic polymers for environmental protection applications. IOP Conference
Series: Materials Science and Engineering, 18 172001.

Mudi, Usman, & Ibrahim. (2015). Clinical and Industrial Application of Organometallic Compounds and
Complexes:A Review. American Journal of Chemistry and Applications, 2(6), 2381-4535.

Pinkus, I. (2017). Organometallic compounds. Retrieved from Chemistry Explained:

http://www.chemistryexplained.com/Ny-Pi/Organometallic-Compounds.html

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