24��inorganic and organometallic polymers

24 Inorganic and organometallic polymers

Derek P. Gates

Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver,

BC, Canada V6T 1Z1

In 2003, numerous advances were made in the area of inorganic polymer science.

In the main group, highlights include the preparation of siloxane nanowires using

gold nanoparticles, the addition polymerization inorganic multiple bonds, and

the development of new s- and p-conjugated polymers. Novel self-assembled

cylindrical ferrocene-containing copolymers were used as precursors to arrays of

ceramic nanostructures. Conjugated polymers have been prepared containing

transition metals such as ruthenium, zirconium and zinc.

1 Introduction

The development of polymers composed of main group elements or transition metals

attracts interest from researchers in main group, organometallic, polymer, and

materials chemistry. Researchers are motivated by the challenges associated with

developing new synthetic methodologies, and the prospect of finding materials

possessing unusual properties and possible specialty applications.

This article shall survey the highlights in the field of inorganic and organometallic

polymer science published in 2003. This year, the format of this article will be

modified slightly from that of previous articles of this series.1–6 The number of sub-

sections will increase from four to eight. A separate section will appear highlighting

new reviews and books that have appeared. The areas of silicon–oxygen polymers and

macromolecules containing catenated Group 14 elements will now comprise two

sections due to the large number of publications in each area. A section will now be

devoted solely to the polyphosphazenes and their derivatives and a separate section

will appear outlining newer main group element-containing polymers. Given the

growth in the number of papers published on ferrocene-containing macromolecules,

advances in these polymers will now be treated separately from other types of d-block

element-containing systems.

Similar to previous articles in this series, an emphasis will be placed on preparative

aspects of inorganic polymer chemistry rather than detailed properties and

morphological studies. The focus will be on linear polymers possessing inorganic

elements within the main chain. However, in some instances novel polymers with

DOI: 10.1039/b312103h Annu. Rep. Prog. Chem., Sect. A, 2004, 100, 489–508 489

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http://dx.doi.org/10.1039/b312103h

http://pubs.rsc.org/en/journals/journal/IC

http://pubs.rsc.org/en/journals/journal/IC?issueid=IC004100

inorganic elements in the side-group structure will also be highlighted. Due to the

recent surge in activity in the field of inorganic dendrimers, there is no longer space to

review these fascinating materials here.

2 Books and reviews of inorganic polymer science

In the past year several books, special issues of journals, and review articles of note

were published in the field of inorganic polymer chemistry. Particularly noteworthy is

a comprehensive book by Harry R. Allcock on the development and applications of

phosphazene polymers.7 This is perhaps the most comprehensive book on this diverse

field. A book on the synthesis and properties of silicones has appeared as a result of a

2001 symposium held at the 221st ACS meeting in San Diego, USA.8 A special

issue of the Journal of Organometallic Chemistry was published to commemorate

the 50th anniversary of the first publication on polysilanes by Makoto Kumada and

co-workers in 1953.9 In addition to original articles, a number of reviews may be

found within this issue.10–13 Another issue of the same journal entitled ‘‘Where

organosilicon chemistry is going?’’ also includes numerous articles on silicon

polymers and materials.14 A book has appeared covering polymers containing metals

and metal-like elements.15 In addition, a book on macromolecules containing metals

and metalloids has been published in Macromolecular Symposia following a

symposium at the 39th IUPAC Congress in Ottawa, Canada.16 There is a special

issue of Coordination Chemistry Reviews on the structure, properties and applications

of inorganic polymers which contains numerous reviews of interest.17

Dyer and Reau have written an interesting review of p-conjugated systems

featuring the heavier elements of Groups 14 and 15.18 This comprehensive review

covers the synthesis and characterization of both molecular and polymeric systems,

including siloles and phospholes, and also includes a nice discussion of the electronic

structure of these systems. A feature article has appeared which reviews recent

research on helical conformations of optically active polysilanes.19 A review on the

applications of polysilanes in semiconductor fabrication has appeared.20 The

synthesis and properties of polysilanes with chains interrupted by heteroatoms has

been reviewed.21 A perspective has appeared outlining the use of metal-catalysis to

construct inorganic rings, chains and macromolecules.22 The use of polymers as

precursors to silicon-based ceramics has been overviewed.23 The use of biodegradable

polyphosphazenes for drug delivery has been reviewed.24 A short review of

poly(cyclodiborazene)s has been published.25

A review of metal alkynyl s-complexes and their use as building blocks for

polymers has appeared.26 Bunz has reviewed recent chemistry involving the

development of carbon-rich organometallic polymers.27 A concept article has been

published outlining strategies for the assembly of metallo-supramolecular block

copolymers.28 A review of organometallic polymers with interesting redox properties

and potential use catalysis has appeared.29 Manners has briefly reviewed the use of

polyferrocenylsilanes in photonics and nanolithography.30 A special issue of Comptus

Rendus Chimie on dendrimers and nanosciences contains several articles on inorganic

systems and may be of interest.31

490 Annu. Rep. Prog. Chem., Sect. A, 2004, 100, 489–508

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3 Polysiloxanes (silicones) and related polymers

Silicone polymers continue to be the subject of numerous research papers and patents

in the past year, and this section will focus primarily on preparative and mechanistic

aspects in silicone chemistry. There is considerable interest in the synthesis of vinyl-

substituted polysiloxanes due to the additional chemical functionality vinyl groups

provide to the polymer. For example, a general route to interesting comb-, star-, and

dendritic-branched polysiloxanes has been reported.32 The novel strategy to these

materials uses anionic ring-opening polymerization (ROP) of cyclic trisiloxanes

containing vinyl substituents. In one case, a comb-like polymer with uniform

branches (i.e. 3comb) was assembled using the living anionic ROP of VD2 to give

polymer 1 (Mn ~ 4600 g mol21; PDI ~ 1.12) with a regularly spaced vinyl

substituent (ca. 19 in each polymer). Hydrosilylation with Me2ClSiH using

chloroplatinic acid yields chlorosilyl-polymer 2. The grafts (branches) were

introduced by treating 2 with living siloxane polymer 3; a gradient copolymer of

VD2 and D3 (Mn ~ 2300 g mol21) with approximately five vinyl groups in each

macromolecule. Interestingly, the molecular weight of 3comb estimated using GPC

(Mn ~ 19,600 g mol21; PDI ~ 1.46) was lower than expected (43,000 g mol21). This

arises because of the different hydrodynamic behavior of the branched macro-

molecule and the linear standard. Molecular weights determined using multiangle

light-scattering (MALS) were very close to expected values. Several other polymer

architectures (i.e. irregular combs, stars and dendrimers) were produced using a

similar strategy, however, D3 and V3 were used in addition to VD2. Anionic ROP of

combinations of V3, VD2, D3 and PD2 gave homo- and co-polymers which were

grafted to modified silica surfaces and their use as supported Pt-catalysts for

hydrosilylation was tested.33

The ROP of vinyl-substituted 2,2,4,4,6,6-hexamethyl-8,8-divinylcyclotetrasiloxane

using cationic and anionic initiators gave copolymers with a 3:1 molar ratio of

dimethylsiloxane and divinylsiloxane.34 Analysis of the polymerization reactions

revealed that mixtures of linear copolymer, low molecular weight oligomers and

monomeric cyclosiloxanes were formed. Detailed assignment of heptads in the 29Si

NMR spectra is reported. Analysis of these new polymers using DSC revealed glass

transitions (Tg’s) between 2121.6 and 2125 uC and the TGA showed that these

materials are thermally stable to 350 uC and give ceramic yields of 70% above

600 uC. Whilst anionic initiation using a phosphazene superbase gives a polymer

with a random microstructure, the triflic acid initiated ROP yields a copolymer with

a more ordered microstructure. Similar findings were obtained in the analysis of

the microstructure of polymers produced from the cationic and anionic ROP of

2,2,4,4,6,6-hexamethyl-8,8-diphenylcyclotetrasiloxane.35

Polymer electrolytes based on cross-linked polysiloxanes with poly(ethyleneglycol)

substituents have been reported.36 A soluble precursor 6 (n:m ~ 1:30) was prepared

by hydrosilylation of poly(methylhydrosiloxane) 5 with vinyl substituted oligo-

(oxyethylene)s. The soluble precursor polymer 6 was cross-linked using diallyl-

substituted polyethylene glycol in a series of steps involving high vacuum and

subsequent heating to remove solvent. Analysis of the films by infrared and NMR

spectroscopy revealed that no Si–H groups were present in the cross-linked materials.

Annu. Rep. Prog. Chem., Sect. A, 2004, 100, 489–508 491

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The conductivity of films prepared with the optimal ethylene oxide/lithium ratio

(20:1) were 1.33 6 1024 S cm21 at 25 uC and slightly higher at elevated temperature.

A lithium battery has recently been constructed using these materials and

LiNi0.8Co0.2O2.37 Proton conductive composites of polydimethylsiloxane and

zirconium oxide containing phosphotungstic acid with a conductivity of 5 6 1025

S cm21 at 150 uC have been reported.38

The synthesis and photophysical properties of silicones containing fluorescent side-

groups has been reported.39 The fluorescent polymers 7a–f were prepared using the

rhodium catalysed dehydrocoupling of poly(methylhydrosiloxane) 5 and a variety

of fluorescent alcohols or phenols. The polymers were characterised using 29Si- and1H-NMR spectroscopy, and by UV-vis and fluorescence spectroscopy. Interestingly,

the 29Si NMR signals observed for 7d and 7e (grafted with 8-hydroxyquinoline and

8-hydroxyquinaldine) are shifted upfield with respect to that for the other polymers.

This was attributed to weak coordination of nitrogen atoms in the substituent to

silicon. A photorefractive composite material for reversible data storage was

prepared using carbazole-substituted polysiloxane as the photoconducting medium.40

The exciting catalytic formation of siloxane-containing nanowires by using gold

nanoparticles was reported by Klabunde and co-workers.41 Digestive ripening

experiments of large polydisperse Au-ketone-stabilised colloids with the silane


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(C18H37SiH3) were used to form small gold nanoparticles with a narrow size

distribution. During the reaction a weak Au–Si bond is formed accompanied by a loss

of hydrogen. Remarkably, when small amounts of water are present during the

digestive ripening in ketone solvent, novel nanowires, filaments and tubes were

observed in SEM photographs. High resolution TEM showed that a gold

nanoparticle is present at the end of each of the nanostructures. The average

diameter of the nanowires was 50–100 nm and lengths are close to a millimeter.

Elemental analysis and energy-dispersive X-ray studies suggest that the composition

of these nanostructure is C18H37SiO1.5 with traces of Au. Structure 8 was proposed to

account for this composition and is mechanistically feasible.


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There has been considerable interest in the preparation of well-defined copolymers

containing silicone moieties using controlled radical polymerization techniques such as

atom transfer radical polymerisation (ATRP) and the reversible addition–fragmentation

chain transfer process (RAFT).42–44 Studies of the cationic ROP of 1,4-dioxatetrasil-

acyclohexane have been conducted in an effort to more fully understand the mechanism

of polymerization of D3.45 The products of n-BuLi and sec-BuLi initiated polymerization

of D3 have been studied using matrix-assisted laser desorption ionization (MALDI) mass

spectrometry.46 The mass spectral peak intensities were monitored to determine the

effects of polymerization time, initiator concentration and temperature on the type of

initiator species present (i.e. Bu(Me2SiO)nMe2SiOLi where n ~ 0,1,2) and the degree of

chain redistribution (i.e. backbiting: 9A10).


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The hydrosilylation copolymerization of the a,v-dihydro-functionalised linear

siloxane 11 with a variety of silicon-containing dienes (i.e. 12) catalysed by Karstedt’s

catalyst has been used to prepare new poly(carbosiloxane)s (i.e. 13).47 Interestingly,

infrared analysis of the polymers revealed that no Si–H end-groups were present in

the polymers and only terminal vinyl groups were present. The Tg’s for the materials

were between 277 and 280 uC which are comparable to that for poly(3,3,3-

trifluoropropyl)methylsiloxane (Tg ~ 270 uC).

Amino end-functionalised polysiloxanes have been used to incorporate C60 into

polysiloxanes.48 Carbon black (CB)–polydimethylsiloxane (PDMS) composites were

studied by automated scanning probe microscopy to determine the effect of CB

concentration and curing rate on roughness and conductivity.49 Hydroxyl-terminated

PDMS vulcanized with Si(OEt)4 was used as a hydrophobic matrix to improve the

activity of the enzyme lipase which was immobilised within it.50 PDMS was also

studied as a coating for controlled drug release.51 A method has been reported to

fabricate complex three-dimensional microfluidic channel systems (i.e. knots, spiral,

braids, grids, etc.) in PDMS.52

4 Polysilanes, polygermanes, polystannanes, polycarbosilanes andrelated polymers

Polymers containing catenated Group 14 elements in the main chain continue to

attract attention due to their exciting electronic properties and their novel methods of

synthesis. Of particular interest, is an essay by Kumada describing his ‘‘chance

discovery’’ of hexamethyldisilane from residues of the Rochow Direct Process which

led to the field of polysilane chemistry.53

An important development in 2003 in the synthesis of polysilanes was the report

that the novel molybdenum complex (14) effectively catalyses the dehydrogenative

coupling of arylsilanes to give polysilanes of moderate molecular weight.54 The exact

mechanism of reaction is not known. However, complex 14 was previously

characterised from the reaction of [MoH4(dppe)2] with PhSiH3. Treatment of 14

with PhSiH3 leads to complex 15 which is stable in the solid state, but reverts to 14

in solution. The authors speculate that the transformation of 15 to 14 involves

the release of the silylene ‘‘PhSiH’’. Remarkably, if complex 14 is exposed to

excess PhSiH3 (ca. 200 equiv.) at 120 uC for 24 h, polysilane 17 is formed. The

mechanism of chain growth is unclear, however, presumably silylene ‘‘PhSiH’’ inserts

into the Si–H bond of growing polymer 16 (n ~ 1, 2, 3, 4, etc.). GPC analysis

of samples of 17 gave a monomodal molecular weight distribution distribution

(Mw ~ 9150 g mol21; PDI ~ 3.02). These results are comparable to those obtained

with early Group 4 catalysts. The dehydrogenative coupling of primary alkyl silanes

(n-octylsilane and n-dodecylsilane) using Wilkinson’s catalyst has led to oligomers of

up to 5–6 silicon atoms.55 Low molecular weight polyvinylsilanes, [CH2CH(SiH2Ph)]nand [CH2CH(SiH3)]n were prepared and cross-linked using a dehydrocoupling

catalyst.56

The anionic polymerisation of a ‘‘masked disilene’’ containing an amine substituent

(18) leads to a new functional polymer 19.57 Interestingly, the polymerization

proceeds with a high degree of regioselectivity. The amino substituents could be


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replaced by chloro substituents by treating 19 with acetyl chloride. Polymer 20 was

only slightly soluble, however after nucleophilic substitution soluble polysilanes (21,

22, and 23) were obtained that had molecular weights (ca. 1.56 104 – 3.36 104 g mol21)

close to the calculated molecular weights (based on 18 : BuLi ratio). The preparation

of H-substituted polysilane 24 was not possible using direct reduction of chloro-

substituted 20 with LiAlH4, however, reduction of the ethoxy-substituted polysilane

yielded 24 without any degradation of the backbone. The role of oligomers in the

Wurtz coupling of MePhSiCl2 using Na revealed that a dimer plays a key role in this

reaction.58

Triblock copolymers have been prepared from polysilanes end-functionalised

with a group possessing a C–Br bond that can function as macroinitiators for

ATRP.59 Using this strategy poly(methylmethacrylate)-b-poly(methylphenylsilane)-

b-poly(methylmethacrylate) copolymers with molecular weights between 9,000 and

50,000 g mol21 and narrow polydispersities (1.6–2.7) were prepared. Using an

analogous ATRP strategy, the same group has prepared ABA triblock copolymers

(A ~ poly(hydroxyethyl methacrylate) or poly[oligo(ethyleneglycol) methyl ether

methacrylate]; B ~ poly(methylphenylsilane).60 TEM studies of the copolymers in

water revealed that micelles were formed along with larger aggregates (300–1000 nm).

A series of end-lithiated polysilanes 26 were prepared from the BuLi initiated

polymerization of 25.61 Reaction of 26 with functionalised silica 27 gave end-grafted

polysilanes 28. The thermochromic and solvatochromic properties of the end-grafted

polymer were examined as a function of side-group structure, temperature and

solvent.


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Tamao and co-workers have prepared a series of conformationally restricted oligo-

silanes with four to ten silicon atoms in an effort to gain insight into the conforma-

tional dependence of s-conjugation in polysilanes.62 An X-ray crystallographic study


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showed that the hexasilane 30 had the expected cisoid-anti-cisoid (CAC) conforma-

tion and, by extension, it was assumed that 31 must have a CACAC conformation.

Remarkably, UV/Vis studies of the oligomers reveal that, regardless of chain length, a

single ss*-transition (ca. 240 nm) is observed corresponding to absorption derived

from the anti fragment. Compound 29 which does not contain an anti fragment shows

no absorbance at 240 nm. For unconstrained polysilanes the lmax is red-shifted as

the chain length increases. Significantly, this work provides clear-cut evidence that the

s-conjugation in polysilanes does not extend through tetrasilane fragments with

small dihedral angle (i.e. cisoid) and is primarily through anti fragments.

The study of optically active polysilanes continues to attract considerable

attention. Sanji, Tanaka and co-workers have reported the first example of induced

activity of short-chain oligosilanes within the internal cavity of c-cyclodextrins.63 The

first optically active polygermanes (32 and 33) have been prepared using the

demethanative coupling of RMe2GeH mediated by a ruthenium catalyst.64 Molecular

weights around 10,000 g mol21 were obtained and the germane polymers were shown

to have lower screw sense selectivity than analogous polysilanes. A series of

polystannanes bearing mesogenic side-chains have been prepared by the Wurtz

coupling.65 The polymers obtained had high molecular weights (ca. 105 g mol21).

Moderate molecular weight (4000–6000 g mol21) polymers and copolymers (i.e. 34)

containing tetraphenylsilole or tetraphenylgermole with Si–Si, Ge–Ge, and Si–Ge

backbones have been prepared using Wurtz-type coupling.66 Remarkably, fluores-

cence quenching studies revealed that these polymers are promising sensors for

nitroaromatic analytes (i.e. 2,4,6-trinitrotoluene, TNT, picric acid).

Highly strained silacyclopropanes have been prepared and their anionic ROP using

BuLi in the presence of HMPA leads to low molecular weight polymers 35 (R ~ tBu;

R’ ~ sBu or tBu; Mn ~ 1400–2100 g mol21) of high hydrophobicity.67 The synthesis


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of cyano-substituted poly(silylenemethylene) [Si(CN)(Me)CH2]n has been reported

using the post-polymerisation modification of [Si(Cl)(Me)CH2]n.68 Interestingly, the

new cyano polymer exhibited a Tg at 33 uC which was considerably lower than

poly(methacrylonitrile) (Tg ~ 120 uC). A similar post-polymerisation modification of

[Si(Cl)(Me)CH2]n using alkyl- or aryl-substuted alcohols in the presence of base was

used to prepare comb-like polycarbosilanes.69 Amphiphilic diblock copolymers of

poly(diethylsilacyclobutane) as the hydrophobic segment and sulfonated poly(acrylic

acid) have been prepared.70

ADMET polymerization has been used to prepare functionalised polycarbo-

silanes.71 s-p-Conjugated polymers 36 with oligosilane and [2.2]paracyclophane

units in the main chain have been prepared.72 The conjugation in these polymers

was studied by using UV/Vis absorbance and photoluminescence spectroscopy.

Macromolecules containing chiral disilane moieties spaced by arylethynyl

groups have been prepared and their solution optical properties measured.73

Poly(silylenearylenevinylene) polymers have been prepared using hydrosilylation

polymerization.74

5 Polyphosphazenes, polyheterophosphazenes and related polymers

High molecular weight poly(dichlorophosphazene) [NPCl2]n was prepared in one-pot

by refluxing a mixture of PCl5, NH4Cl, CaSO4?2H2O (0.125%) and HSO3(NH2)

(0.25%) in 1,2,4-trichlorobenzene for approximately 3.5 h.75 The polymer was

isolated in ca. 30% overall yield (based on PCl5) after precipitation into hexane and

drying. Unfortunately, scaling up the reaction (w100 g PCl5) led to a number of

problems and on occasion small explosions occurred. Nevertheless, in small scales the

isolated [NPCl2]n could be treated with 2,2,2-trifluoroethanol in the presence of

Cs2CO3 to afford air-stable [NP(OCH2CF3)2]n which had a molecular weight on the

order of 106 g mol21 as estimated by GPC.

There continues to be considerable interest in the macromolecular substitution

chemistry of polyphosphazenes. An alternative method to prepare mixed-substituent

polyphosphazenes 39 through side group exchange has been described by Allcock and


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co-workers.76 It was found that when polymers 37 (R ~ OCH2CF3, OCH2(CF2)2H,

OCH2(CF2)4H) were treated with THF solutions of sodium ethoxide, sodium

propoxide, sodium isopropoxide and sodium hexoxide at room temperature or reflux

partial replacement of the fluoroalkoxy substituents with alkoxy substituents

occurred. Up to 60% substitution was observed after treating 37 (R ~ OCH2CF3)

with NaOCH2CH3. Interestingly, lower degrees of substitution were observed for 37

(R ~ OCH2(CF2)2H, OCH2(CF2)4H). In all cases, the substitution was accompanied

by a dramatic decrease in molecular weight for the resultant polymers 39. This was

attributed to a decrease in the mass of the side groups and smaller hydrodynamic radii

of the mixed substituent polymers rather than backbone degradation. It was not

possible to replace substituents in alkoxy-substituted polymers 37 (R ~ OEt, OnPr,

OiPr, OHex). Presumably, the lower electron-withdrawing ability of the alkoxy

substituents vs. the fluoroalkoxy substituents render the phosphorus less susceptible

to nucleophilic attack. The proposed mechanism of macromolecular substitution

involves the 5-coordinate intermediate 38.

Macromolecular substitution has been used to prepare polyphosphazenes bearing

the amino acid tyrosine and their hydrolytic degradation, pH-sensitive solubility and

ability to form hydrogels on exposure to Ca21 ions were studied.77 Mixed substituent

polyphosphazenes containing the chiral substituent (R)-1,1’-binapthyl-2,2’-dioxy and

amine or aryloxy substituents have been prepared from [NPCl2]n.78 Degradable

water-soluble polyphosphazenes bearing carboxylatophenamino groups have been

prepared and their potential use in controlled drug release has been studied.79

Biodegradable polyphosphazenes have been prepared with acrylate side groups which

facilitates micro-cross-linking of the polymer.80 The synthesis and characterization of

polyphosphazenes bearing Cp*Fe(dppe) groups appended to the side-chain structure

have been reported.81

Polymer 40, a modified sol–gel precursor of poly[bis(methoxyethoxyethoxy)-

phosphazene] (MEEP), has been prepared and cross-linked by hydrolysis and

condensation of the siloxy groups.82 The cross-linked inorganic–organic hybrid

networks formed stable hydrogels and their dye-release abilities were examined.

Amorphous polyphosphazenes bearing chlorinated- and fluorinated- aryloxy- and

alkoxy- side-groups have been prepared and found to possess controlled refractive

indices between 1.3889 and 1.5610.83


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Thermosensitive poly(ethylene oxide)–MEEP block copolymers were prepared

using the controlled, PCl5-initiated, cationic polymerisation of phosphoranimines from

amine terminated poly(ethylene oxide).84 After cross-linking using c-irradiation, a

water-swellable hydrogel was formed which showed temperature dependent water

uptake and had swelling values higher than MEEP homopolymers.

Polyphosphazenes are known to possess flame-retardant properties. An interesting

study of the flammability of inorganic polymers, including polysilphenylene-siloxane

and polyphosphazenes has been conducted.85 Remarkably, polyphosphazene rubber

had a four times lower peak heat release rate than the polyurethane elastomer

currently in use in aircraft seat cushions.

6 Other main group element-containing polymers

There continues to be significant activity in the development of new classes of

polymers containing main group elements in the main chain. The synthesis of

polyphosphinoboranes 42 (R ~ Ph, iBu, p-nBuC6H4, p-dodecylC6H4) from the

rhodium-catalysed dehydrocoupling of the appropriate phosphine–borane adduct

41.86 This reaction afforded polymers of moderate to high molecular weight and

very broad polydispersities as determined using static and dynamic light scattering

and/or GPC. The stability of the B–P backbone was evaluated by exposing the

polymer to amines and phosphines and no appreciable degradation was detected.

The polymers had low Tg’s (41: R ~ iBu, 5 uC; R ~ p-nBuC6H4, 8 uC; R ~

p-dodecylC6H4, 21 uC) and wide-angle X-ray scattering showed that the polymers

were amorphous. TGA analysis of the new polymers revealed that weight loss began

between 150 and 160 uC depending on substituents and high ceramic yields were

obtained after heating to 1000 uC.

The first addition polymerization of PLC bonds has been reported to give new

phosphine polymers with alternating phosphorus and carbon atoms in the main

chain.87 Despite its success in organic polymer chemistry, addition polymerization

has often been dismissed as a method to prepare inorganic macromolecules. The

choice of a kinetically stable phosphaalkene 43 was a key to the development of this new

methodology. Monomer 43 was polymerised during distillation (without initiator) or

when heated with a radical or anionic initiator. Poly(methylenephosphine)s 44 with

number average molecular weights (Mn) between 5000–12,000 g mol21 and narrow

polydispersity indices (v1.3) were obtained (light-scattering showed that GPC

underestimates the molecular weight). Functional polymer 44 was easily oxidised to

45 and 46 by treating it with elemental sulfur or hydrogen peroxide (or oxygen),

respectively. TGA analysis of 46 revealed that the polymer had high thermal stability

of weight loss with an onset at 320 uC.

Protasiewicz and coworkers have outlined an alternate synthesis to poly(p-

phenylenephosphaalkene)s; p-conjugated polymers with PLC bonds in the main

chain.88 A phospha-Wittig reagent was prepared in situ by the reduction of 47

(Ar ~ 4-tBuC6H4) with Zn in the presence of PMe3. Reaction of the phospha-Wittig

reagent with various dialdehydes 48 (linker ~ 1,4-phenylene, 2,5-thienyl, 1,1’-ferrocenyl) afforded insoluble E-poly(p-phenylenephosphaalkene)s 49. However,

employing a n-hexyloxy-substituted 1,4-phenylene linker in the aldehyde afforded a


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soluble orange polymer. The molecular weight (Mn) was estimated at 6500 g mol21

(i.e. in 49, n ~ 6) using end group analysis. The absorbance band maximum for the

soluble polymer 49 (lmax ~ 445 nm) was identical to the small molecule models,

suggesting that the presence of the bulky 2,3,5,6-tetraaryl-substituted phenylene

spacer might partially disrupt the p-conjugation. Remarkably, the polymer was

fluorescent and an emission maxima was observed at 545 nm. This is the first time

fluorescence has been reported for a poly(p-phenylenephosphaalkene).

New p-conjugated phosphole polymers 50 with a variety of aryl spacer groups have

been prepared using the Heck-Sonogashira reaction.89 Molecular weights (Mn)


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between 7000 and 10,000 were obtained for the polymers which showed photo-

luminescent properties. Although not a polymer, short chain phosphole oligomers

have been used to make a light-emitting diode.90 Hyperbranched poly(phenylene-

silolene)s have been prepared.91 Four new organoboron polymers 51 with fluorescent

properties have been prepared using a Sonogashira coupling strategy.92 Ion

conductive polymers have been prepared containing boron atoms in the main chain.93

7 Ferrocene-containing polymers

Support for a ring-slippage mechanism for photolytic ROP of phosphorus-bridged

ferrocenophane 52 has been obtained.94 Irradiation of solutions of 52 in the presence

of excess P(OMe)3 yielded ring slippage product 53 [L ~ P(OMe)3] which was

characterised crystallographically. Complex 53 was found to polymerise when heated

in THF solution. Based on these results a possible mechanism of polymerization was

proposed where 53 (L ~ THF) first undergoes intermolecular combination to give 54

which has a free Cp2 tail which can begin propagation.

Polyferrocenylsilanes possessing Co2(CO)6 groups (55) in the side-group structure

were prepared by post-polymerisation reaction of an acetylenic-substituted polymer

with Co2(CO)8.95 Heating 55 in a tube furnace to 600 or 900 uC gave black ceramics

that were found to contain a Si/Fe/Co ratio of 1:1:2 by EDX. TEM analysis showed

that the sample contained electron-rich metal nanoparticles and magnetic measure-

ments showed that samples prepared at 600 uC were superparamagnetic while those

prepared at 900 uC were either ferromagnetic or superparamagnetic. Block

copolymers of polystyrene and polyferrocenylsilane were found to self-assemble in

thin films to generate nanoscopic cylinders orthogonal to the substrate surface.96

Pyrolysis of the films can generate patterned arrays of ceramic nanostructures.

Polyisoprene-b-ferrocenyldimethylsilane was prepared by living anionic polymeriza-

tion and self assembled in hexane solution to yield cylinders with a ferrocene core.

Shell cross-linking was performed by metal-catalysed hydrosilylation of the pendant

vinyl groups of the isoprene using O(SiMe2H)2.97 Pyrolysis of the shell cross-linked

ceramics gave Fe nanoclusters which retained the cylindrical shape.

When films of asymmetric polyferrocenyldimethylsilane-b-polydimethylsiloxane 56

(n ~ 900, m ~ 90, PDI ~ 1.01) were grown by solvent casting the copolymer self-

assembles to form cylinders of the longer PDMS block surrounded by a shell of

ferrocenylsilane.98 It was postulated that the stiffer ferrocenylsilane may thermo-

dynamically prefer to be on the surface of the cylinder to minimize curvature. In a

separate study, block copolymer 56 (n ~ 40, m ~ 480, PDI ~ 1.01) in decane solution

was found to show a dramatic temperature dependent morphology transition from

nanotubes at 23 uC to short rods at 50 uC and back to nanotubes when cooled.99

The miktoarm copolymer 57 has been prepared by quenching the living anionic

polymerization of the [1]ferrocenophane fcSiMe2 followed by quenching with SiCl4and subsequent substitution of the remaining Si–Cl bonds with living polyisoprene

(PI).100 The transition metal-catalysed ROP of fcSiMe2 in the presence of silanes

such as ClMe2SiH leads to polyferrocenylsilane with a chlorosilyl end-group.101

Interestingly, treating the functional polymer with commercial polyethylene glycol

resulted in the formation of novel telechelic polymers that were water soluble. Water


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soluble polyelectrolytes were prepared by treating 3-iodopropyl Si-substituted

polyferrocenylsilane with various nucleophiles.102

Silica microspheres in a matrix of cross-linked polyferrocenylsilane has been used

to construct a photonic crystal device.103 Novel poly(ferrocenylenesilyne)s have been

prepared from the reaction of dilithioferrocene?TMEDA with trichloroalkyl-

silanes.104 When small alkyl substituents were used (methyl, vinyl), the polymers

were partially soluble whereas employing long chain alkyl (C ¢ 8) substituents led to

soluble film forming polymers. The hyperbranched polymers could be pyrolysed to

give Fe/Si/C ceramics.

8 Polymers containing skeletal d-block elements

A novel organometallic conducting polymer containing ruthenium in the backbone

(58) has been prepared.105 GPC analysis of the polymer showed that the molecular


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weight was up to 2 6 104 g mol21 (i.e. n ~ 40). The polymer undergoes a reversible

reduction and the reduced form exhibits a ferromagnetic interaction between the

ruthenium sites.

The regioselective zirconocene coupling of alkynes gives novel p-conjugated

polymers 59 (ArF ~ C6H5).106 The zirconium moiety was easily replaced by reaction

with S2Cl2 to give a thiophene polymer (Mw ~ 11840 g mol21) or the Zr could be

removed with H1 to leave a –CHLC(ArF)–C(ArF)LCH– spacer (Mw ~ 9260 g mol21).

New poly(salphenyleneethynylene)s 60 (M ~ Zn, Ni, VO) have been prepared

using a Sonogashira coupling route.107 The molecular weights of the polymers were

estimated using GPC (M ~ Zn, Mw ~ 37,000; M ~ Ni, Mw ~ 17,000; M ~ VO,

Mw ~ 84,000 g mol21). The polymers were found to be weakly luminescent. New

p-conjugated porphyrin polymers were prepared and their complexes with zinc(II),

lead(II) and copper(II) were formed.108 New high molecular weight platinum(II) poly-

yne polymers incorporating substituted 1,4-diethynylbenzene derivatives have been

prepared.109 The first examples of soluble mercury(II)-containing poly-ynes have been

prepared and their optical properties have been studied.110

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and I. Manners, Adv. Mater., 2003, 15, 51.96 K. Temple, K. Kulbaba, K. N. Power-Billard, I. Manners, K. A. Leach, T. Xu, T. P. Russell and

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12686.98 J. Raez, Y. Zhang, L. Cao, S. Petrov, K. Erlacher, U. Wiesner, I. Manners and M. A. Winnik, J. Am

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100 X.-S. Wang, M. A. Winnik and I. Manners, Macromol. Rapid Commun., 2003, 24, 403.101 A. Bartole-Scott, R. Resendes and I. Manners, Macromol. Chem. Phys., 2003, 204, 1259.102 M. A. Hempenius, F. F. Brito and G. J. Vancso, Macromolecules, 2003, 36, 6683.103 A. C. Arsenault, H. Miguez, V. Kitaev, G. A. Ozin and I. Manners, Adv. Mater., 2003, 15, 503.104 Q. Sun, K. Xu, H. Peng, R. Zheng, M. Haussler and B. Z. Tang, Macromolecules, 2003, 36, 2309.105 M. Kurashina, M. Murata, T. Watanabe and H. Nishihara, J. Am Chem. Soc., 2003, 125, 12420.106 S. A. Johnson, F.-Q. Liu, M. C. Suh, S. Zurcher, M. Haufe, S. S. H. Mao and T. D. Tilley, J. Am Chem.

Soc., 2003, 125, 4199.


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107 A. C. W. Leung, J. H. Chong, B. O. Patrick and M. J. MacLachlan, Macromolecules, 2003, 36,5051.

108 T. E. O. Screen, J. R. G. Thorne, R. G. Denning, D. G. Bucknall and H. L. Anderson, J. Mater. Chem.,2003, 13, 2796.

109 M. S. Khan, M. R. A. Al-Mandhary, M. K. Al-Suti, T. C. Corcoran, Y. Al-Mahrooqi, J. P. Attfield,N. Feeder, W. I. F. David, K. Shankland, R. H. Friend, A. Kohler, E. A. Marseglia, E. Tedesco,C. C. Tang, P. R. Raithby, J. C. Collings, K. P. Roscoe, A. S. Batsanov, L. M. Stimson and T. B. Marder,New J. Chem., 2003, 27, 140.

110 W.-Y. Wong, L. Liu and J.-X. Shi, Angew. Chem. Int. Ed., 2003, 42, 4064.


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24��inorganic and organometallic polymers

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