22 inorganic and organometallic polymers

22 Inorganic and organometallic polymers

Derek P. GatesDOI: 10.1039/b408311n

In 2004, numerous advances were made in the area of inorganic polymer

science. In particular, evidence for the presence of Si–H end groups

from the Wurtz coupling of dichlorosilanes was obtained. A new

mechanism of dehydropolymerization of stannanes was proposed. The

first p-conjugated polymers featuring PLP bonds in the main chain

were prepared. In the area of transition metal macromolecules, the first

examples of ruthenocenylsilane and bis(benzene)chromium polymers

have been obtained by using ring-opening polymerization techniques.

Silametallacyclobutanes have been polymerized. In addition, the photolytic

living anionic ring-opening polymerization of silicon bridged [1]ferro-

cenophanes has been reported.

1 Introduction

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

continues to attract 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 from the 2004 literature. For highlights from previous years the

reader is referred to previous articles in this series which is now in its fifteenth

year.1–14 This article consists of this introduction and seven subsections. The first

subsection will highlight recent reviews and books that have been published in the

area. The next three subsections are devoted to the well-established polysiloxanes,

polysilanes and polyphosphazenes and related polymers. The following section

will highlight recent developments in the preparation of new classes of polymers

composed of main group elements. The article will close with two sections

summarizing recent progress in the areas of ferrocene-containing and related

organometallic macromolecules and polymers containing skeletal d-block elements.

There is no longer space in this article to discuss the recent developments in the

interesting field of solid state coordination polymers unless the polymeric structure is

retained in solution.

In line with 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 inorganic elements in the side-group structure will also be highlighted. The

fascinating and growing field of inorganic dendrimers will not be covered here.

Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC,Canada V6T 1Z1

REVIEW www.rsc.org/annrepa | Annual Reports A

452 | Annu. Rep. Prog. Chem., Sect. A, 2005, 101, 452–471

This journal is � The Royal Society of Chemistry 2005

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View Article Online / Journal Homepage / Table of Contents for this issue

http://dx.doi.org/10.1039/b408311n

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

http://pubs.rsc.org/en/journals/journal/IC?issueid=IC005101

2 Books and reviews of inorganic polymer science

A comprehensive monograph entitled Synthetic Metal-Containing Polymers

was published in 2004.15 The book, authored by Ian Manners, is fully referenced

and will serve as an outstanding reference for researchers active in the field

and would be equally useful as a textbook for a senior level course. Gleria and

de Jaeger have edited several books on cyclic and polymeric phosphazenes

which feature chapters by many of the leading researchers in the field.16–19 A

special issue of Macromolecular Symposia has appeared which contains a number

of interesting reviews in the area of organometallic and coordination clusters

and polymers.20

Several reviews and highlight articles have appeared in the area of main group

element-containing polymers. An article on the unusual chemistry of silicone grease

(Me2SiO)n has appeared and is a very interesting read.21 A review of the biomedical

applications of commercial polymers has a section on the uses of silicones.22 An

excellent review has been published that covers dehydrocoupling of hydrosilanes as

a route to oligomeric- and polymeric-silanes.23 In the area of phosphorus–nitrogen

polymers, two reviews of fluorinated polyphosphazenes and an account of the

development of polymer-supported catalysts containing cyclophosphazenes have

appeared.24–26 In addition, an account has been published which highlights

recent developments in the development of nanomaterials based on phosphorus

dendrimers.27 There is an interesting review outlining the use of organoboron

compounds and polymers in optoelectronics.28

A feature article has appeared highlighting recent developments in the

area of conducting metallopolymers.29 The chemistry of porous coordination

polymers has been reviewed in detail.30 Two reviews dealing with recent

developments in the synthesis of polymers and supramolecular systems based on

terpyridine metal complexes have been published.31,32 A highlight featuring

several metal-containing polymers has been published which outlines recent

advances in the area of polymer-immobilized homogeneous asymmetric catalysis.33

A mini-review covering the development of organic–inorganic hybrid polymers

containing polyoxometallate clusters within the backbone and side-chain has

appeared.34 An account of the recent developments in using coordination-directed

self-assembly of polymers through the formation of quinonoid p-complexes has

been published.35

3 Polysiloxanes (silicones) and related polymers

Being the most widespread class of inorganic polymer, the silicone macro-

molecules continue to be the subject of numerous investigations over the past year.

There is not enough space to highlight all the developments in this vast area.

Therefore, in this section emphasis will be placed on preparative aspects of silicone

chemistry.

Interesting polycarboranesiloxane alternating and block copolymers have been

prepared using a condensation polymerization route.36 The alternating copolymers

were prepared using the two-step process outlined below which involved initial

condensation of the dilithiocarborane (1) with trisiloxane (2) to give 3, which was

subsequently treated with dilithiodiacetylene. Low molecular weight hybrid

polymers (4) were obtained (Mw = 3 000–9 000) which possessed trisiloxane :

carborane : diacetylene molar ratios of 10 : 9 : 1, 5 : 4 : 1 and 3 : 2 : 1. DSC analysis of

Annu. Rep. Prog. Chem., Sect. A, 2005, 101, 452–471 | 453


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4 revealed a broad exotherm around 275 uC and was consistent with diacetylene

crosslinking. The thermal properties of these elastomeric cured networks were also

studied. Crosslinked polysiloxanes were obtained by hydrosilylation of Si–H

functionalized star polysiloxanes with unsaturated epoxides which could later be

subjected to photo-acid catalyzed crosslinking.37 Hydrosilylation of Si–H end-

functionalized polydimethylsiloxane (PDMS) was used as a means to access

carbohydrate functionalized silicones.38

The synthesis of ion conductive networks based on polysiloxanes continues to

attract attention.39–43 In one study, polymethylhydrosiloxane (5, Mw = 1 500–1 900)

was first treated with allyl-functionalized oligo(ethylene glycol) (6, p = 3, 5 or 7) to

yield polymer 7 (m/n = 6, 10, 14, 30 or 38).39 The soluble precursors were crosslinked

by 8 (q = 6, 13 or 23) in the presence of a platinum catalyst and lithium

bis(trifluoromethylsulfonyl) imide as a dopant (EO/Li+ = 32, 24 or 20). The

conductivities of all of the resultant crosslinked polymer matrices were measured and

the maximum conductivities ranged from 2.50 6 1025 to 1.62 6 1024 S cm21.

LiClO4 doped epoxide-crosslinked polysiloxane/polyether electrolytes were studied

by DSC, ionic conductivity and 7Li NMR spectroscopy.40 In particular, the solid

state MAS 7Li NMR spectral results provided evidence for at least two distinct Li+

local environments.

Dehydrogenative coupling of polymeric hydrosiloxanes (9) and ferrocenemethanol

(10, R = H or Me) to yield new ferrocene-containing polysiloxanes (11) was

accomplished using Wilkinson’s catalyst.44 Hydrosilylation of poly(methylhydro-

siloxane) has been used to incorporate cholosteric mesogens into the side-chains of

polysiloxanes.45 These elastomers exhibit liquid crystalline phases over a wide

temperature range. The introduction of chlorobenzyl side-groups into siloxane

homo- and co-polymers has provided access to new functional polymers that

can later be chemically modified to incorporate azobenzene groups or used as

macroinitiators for atom transfer radical polymerization (ATRP).46 Dye-molecular

imprinted polysiloxanes have been prepared and their properties studied.47

Polysiloxanes bearing indole and carbazolyl side groups have been prepared which

exhibit second-order nonlinear optical properties.48



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Ring-opening polymerization (ROP) of cyclic siloxanes continues to attract

considerable attention since this method provides a convenient route to well-defined

silicone polymers and copolymers.49–55 The anionic ROP of 12 (D3) gives living

polymer 13 which can subsequently be used as an initiator for the ROP of

3-chloropropyl-substituted siloxane 14.49 The resultant diblock copolymer 15 can be

treated with 2-hydroxyethyldimethylamine to yield ionic polymer 16 which contains

quaternary ammonium moieties. Copolymers where more than ca. 30% of the

siloxane units are functionalized with hydroxyalkylammonium groups are water-

soluble although at high concentration micelles were formed. Narrow polydispersity

amphiphilic poly[dimethylsiloxane-block-oligo(ethylene glycol) methyl ether metha-

crylate]s have been prepared by quenching living 13 with a bromoorgano-

functionalized chlorosilane which was subsequently used as a macroinitiator for

the ATRP of a glycol-containing acrylate.50

The living anionic block copolymerization of 12 and vinylmethylsiloxane in a

one-pot procedure affords block copolymers 17 with narrow polydispersity.51

The vinyl substituents of 17 were conveniently converted to epoxide-containing

polysiloxanes 18 using MCPBA. The epoxide functionality in 18 served as a useful

functional group to access polysiloxanes with amine, ester, alcohol, ether and

carboxylic acid side groups. In a separate paper, vinyl-substituted block copolymer

17 was partially or fully hydrosilylated with trimethoxysilane or triethoxysilane to



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afford copolymers such as 19 (R = Me or Et).52 Interestingly 19 was found to be

suitable for the isolation of non-aggregated superparamagnetic cobalt nanoparticles

with mean particle diameters of 10–15 nm.

Silicones continue to attract attention because of their unique properties and

potential applications. In one interesting study, the reduction of Pd(OAc)2 by

polymethylhydrosiloxane afforded catalytically active Pd nanoparticles.56 The

polymethylhydrosiloxane functions both as a reducing agent as well as a capping

material. Significantly, these new nanocomposites were found to be effective and

recyclable catalysts for the hydrogenation of conjugated aromatic alkenes and

conjugated enones. Vinyl-substituted cinchona alkaloids were hydrosilylated using

polymethylhydrosiloxane and the resultant polymers were found to be effective

ligands for heterogeneous and homogeneous osmium tetroxide catalyzed asymmetric

dihydroxylation of olefins.57



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An end-hydroxylated PDMS containing polyethylene glycol was partially

crosslinked with alkoxysilanes to afford film coatings that are effective in controlled

drug release.58,59 Poly(e-caprolactone)–poly(dimethylsiloxane) di- and tri-block

copolymers were used to encapsulate nanoparticles of biologically active com-

pounds.60 Densely cross-linked silicone nanocapsules filled with water were

prepared from the vesicle supported ROP of octamethylcyclotetrasiloxane in

aqueous solution.61

Tapping mode atomic force microscopy (TM-AFM) was used to study the surface

of cured end-hydroxylated PDMS containing fumed silica nanoparticles (FSN) as

fillers.62 Such nanocomposites of PDMS and FSN are commonly used to impart

good mechanical properties to materials that are used in applications such as

biomedical elastomers. Surprisingly, the TM-AFM studies of certain compositions of

PDMS and FSN revealed that the fumed silica nanoparticles seemed to ‘‘disappear’’.

This disappearance was attributed to the rapid growth of the siliceous phase from

clusters to the reticular scale (i.e. a network).

4 Polysilanes, polygermanes, polystannanes, polycarbosilanes and

related polymers

The chemistry of catenated Group 14 elements, in particular silicon, was the subject

of numerous studies in 2004. In the past year, there continued to be considerable

interest in the chemistry of polysilanes bearing stereochemically active substituents

and their interesting electronic properties and possible applications.63–70 In one

study, a series of enantiopure polysilanes (20–23) were synthesized in which the

substituents were varied systematically and their properties evaluated.63 Circular

dichroism (CD) spectroscopic studies suggested that each of polymers 20–23 adopt

helical conformations with the same helical screw sense in solution. Remarkably,

when a non-solvent (methanol or ethanol) was added to the solution, the polymers

formed aggregates which show oppositely-signed CD spectra. The thermodriven

helix–coil transition in solution and in the solid state has been studied for polysilane

24.64 Thin films of 24 were found to show a second order transition at 247 uC and a

first order transition 28 uC which were attributed to the glass transition and the

helix–coil transition, respectively. The helix–coil transition in the solid state was

highly reversible and these results were discussed in the context of using polysilanes

as chiroptical switches with +1 and 0 states.



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Similar chiroptical switching properties were observed in isooctane solutions of

polysilanes 25 and 26.65 In particular, the potential use of these polymers as switches

and memory devices with re-writable (RW) and write-once read-many (WORM)

modes was considered. Interestingly, the temperature at which the phase transition

(i.e. switching) occurs was very sensitive to molecular weight and could be set within

a range of 40–100 uC by simply controlling the molecular weight of the polymer.

Spin coated or chemically grafted films of optically active polysilane 27 on quartz

were observed to transfer their helical sense to optically inactive rigid rod polysilanes

28 and 29.71 This thermodriven chiropical transfer and amplification was explained

using a ‘‘sergeants’’ (i.e. 27) and ‘‘soldiers’’ (i.e. 28 or 29) model.

The Wurtz coupling of dichlorosilanes (30) is the most widely used method for the

synthesis of high molecular weight polysilanes (31). Careful IR, 1H NMR, 29Si

NMR, and 1H–29Si heteronuclear correlation NMR spectroscopic analysis of

several polysilanes [31: R1 = Me, R2 = –(CH2)2CF3; R1 = n-C10H21, R2 =

–(CH2)3CH(CH3)2; R1 = R2 = n-Hex; R1 = n-Pr, R2 = Me; R1 = n-C10H21, R2 =

(S)-CH2CH(CH3)CH2CH3] prepared using the Wurtz coupling method confirmed



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unambiguously that Si–H end groups were present.72 Surprisingly, Si–Cl, Si–OH

and Si–OR groups, the expected end groups, were not detected in these experiments.

The authors suggest that these observations implicate radical species as the key

intermediates in the polymerization of alkyl-substituted polysilanes. In a separate

study, Wurtz coupling PhMeSiCl2 followed by treatment with bromine was found to

afford halogen end-functionalized poly(methylphenylsilane).73 Interestingly, this

polymer could be end-functionalized with TEMPO and used to initiate the controlled

free radical polymerization of styrene to give an ABA poly(styrene-b-methyl-

phenylsilane-b-styrene) copolymer.

The hydrosilylation of allyl-functionalized benzo-15-crown-5 with a copolymer of

hydrosilane polymer 32 to afford the crown ether-containing polysilane 33 was

reported.74 The ability of polymer 33 to complex metals was evaluated by treating it

with copper(II) acetate. An analogous hydrosilylation strategy was employed to

prepare polysilane–cycloimonium salt 34 from 32.75 Evidence for through-space

Si…F–C interactions in poly(3,3,3-trifluoropropylmethylsilane) has been obtained

from 29Si and 19F NMR and IR spectroscopic studies.76 This polymer possessed

high sensitivity and selectivity for the chemosensing of fluoride ions in nanomolar

concentrations.77

Several studies have been conducted on oligomeric silanes which are relevant to

the higher molecular weight systems. For example, all anti-pentasilanes have been

prepared and UV and MCD spectra as well as X-ray crystallography suggest a highly

s-conjugated system.78 UV spectroscopy and MALDI-TOF mass spectrometry have

been used to analyze anti-cisoid-alternating oligosilanes up to Si22 and the results

suggested that s-conjugation was suppressed by a cisoid turn.79 The addition of

Me2AlCH2PMe2 to [(1-Me-indenyl)Ni(PPh3)Me] was reported to give improved



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activities in the nickel-catalyzed dehydrogenative coupling of PhSiH3.80 Oligosilanols

of the form R2PhSi[Si(OH)Me]nSiR2Ph (n = 1, 2) have been prepared from

R2PhSi[SiClMe]nSiR2Ph.81

Polysilanes have long been investigated as ceramic precursors. The reaction of

poly(chloromethylsilane) with ammonia followed by pyrolysis under argon was

reported as a route to SiC(N) fibers.82 Ordered assemblies of hollow SiC and

filled SiCN nanospheres have been prepared from mixtures of polymethylsilane

and polysilazane.83 A copolymer of MePhSiCl2, Me(H2CLCH)SiCl2 and PhSiCl3synthesized by Wurtz coupling was pyrolyzed with aluminium acetylacetonate and

the evolution of the resultant ceramic structure was studied by solid state NMR,

XRD, SEM and TEM.84

The mechanism of the metal-catalyzed dehydrocoupling of secondary stannanes

has been investigated.85 Detailed spectroscopic studies suggest that the Sn–Sn bond-

forming step in catalytic dehydrocoupling of R2SnH2 may involve direct insertion of

R2Sn into a M–Sn bond. Thus, a new mechanism (Scheme 1) has been proposed for

dehydropolymerization of secondary stannanes.

Hybrid p-phenyleneethynylene siloleethynylene oligomers 35 (n = 0, 1, 2, 3, 4)

have been prepared.86 Interestingly, the tetramer 35 (n = 3) and pentamer 35 (n = 4)

exhibit absorption maxima matching those of the corresponding silole polymers,

thus, establishing the effective conjugation length in these polymers. Dithienosilole

polymer 36 [Mw = 4,300; PDI = 1.40] has been prepared and electroluminescent

devices based on tris(8-quinolato)aluminium(III) (Alq3) as the emitting layer were

fabricated using this polymer as the hole transport material.87 A series of silylene-

spaced copolymers with arylene donor and acceptor spacers were prepared using

the rhodium-catalyzed hydrosilylation of bisalkynes.88 Novel carbosilane polymers

were prepared using the acyclic diene metathesis (ADMET) polymerization of

Si-diolefin-substituted 1,3-disilacyclobutanes.89 The resultant linear polymers

could subsequently be crosslinked by ring-opening reactions of the disilacyclobutane

moieties.

Scheme 1 Proposed mechanism of metal-catalyzed dehydropolymerization of secondary

stannanes.



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5 Polyphosphazenes, polyheterophosphazenes and related polymers

The living cationic polymerization of phosphoranimines provides access to well-

defined phosphazene homo- and co-polymers. Amphiphilic polystyrene-poly[bis-

(methoxyethoxyethoxy)phosphazene] (PS-MEEP) block copolymers (40) have been

prepared and their properties evaluated.90 Living phosphoranimine 37 was prepared

and the polymerization was quenched with phosphoranimine-terminated polystyrene

38 (prepared by living anionic polymerization of styrene; Mn = 5 000; DP = 50;

PDI = 1.2). Following macromolecular substitution of 39, the properties of the

PS-MEEP copolymers 40 were investigated. The length of the polystyrene block

remained constant while the length of the phosphazene block was varied to obtain

copolymers with PS : MEEP ratios between 1 : 0.06 and 1 : 0.86. In aqueous media,

40 was observed to self-associate to form spherical micelles with diameters in the

167–179 nm range. Interestingly, the critical micelle concentrations (cmc) were highly

dependent on the PS : MEEP ratio with much higher cmc’s for copolymers with

higher loadings of MEEP.



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Mono- and di-telechelic polyphosphazenes have been prepared by treating living

poly(dichlorophosphazene) with appropriate alkoxy or aryloxy phosphoranimines.91

The ditelechelic polymers were prepared with a range of molecular weights (ca.

Mn = 10 000–50 000) and narrow polydispersities (PDI = 1.06–1.47). MALDI

mass spectrometric studies were performed and the results were consistent with

the telechelic nature of these polymers. Interestingly, the monotelechelic

polymers containing norbornene were polymerized using ROMP methods to afford

graft copolymers. In a related paper, the copolymerization of a styryl–telechelic

polyphosphazene with methyl methacrylate also afforded novel graft copolymers.92

The presence of the phosphazene grafts significantly lowered the glass transitions

with respect to poly(methyl methacrylate).

Several publications dealing with chiral polyphosphazenes have appeared.93–97

Chiral phosphazene macromolecules containing (g6-p-cymene)(phosphane)-

ruthenium(II) complexes, such as 41, have been prepared and their catalytic activity

examined in the transfer hydrogenation of acetophenone by propan-2-ol.93 All were

catalytically active however no enantioselectivity in transfer hydrogenation was

observed. Analogous ruthenium-containing polyphosphazenes have been prepared

containing Ru-pyridyl rather than Ru-phosphine moieties.94 A series of chiral (42)

and achiral (43) phosphazene random copolymers with cyclic repeating units have

been prepared by substitution reactions of [Cl2PLN]n.95 The molecular weights (Mw)

of copolymers 42 and 43 ranged from 8.4 6 105–1.69 6 106 g mol21 and 6.0 6 105–

1.59 6 106 g mol21, respectively. The manner in which the glass transitions (Tg’s) of

the polymers varied with copolymer composition was consistent with Barton’s

equation for strictly alternating random copolymers.

An interesting mechanistic study of the ring-opening polymerization (ROP) of

hexachlorocyclotriphosphazene (N3P3Cl6) has appeared.98 The authors found that

when the thermal ROP of N3P3Cl6 was performed in a titanium reactor using

diglyme as solvent, polymer cross-linking, which often causes problems at high

monomer conversion, could be prevented.

Macromolecular substitution of polydichlorophosphazene continues to serve as a

very useful method to obtain macromolecules possessing novel properties. For

example, polyphosphazenes bearing a-amino-v-methyl-poly(ethylene glycol) side

chains have been prepared from [NLPCl2]n.99 Interestingly, the polymers showed

sol–gel transition properties in aqueous solution and they degraded under

physiological conditions making them of interest for applications in drug delivery.

Sulfonated polyphosphazenes have been prepared in a single step without polymer

degradation by protecting the sulfonic acid groups of hydroxybenzenesulfonic acid

as hydrophobic ammonium salts.100 Second-order nonlinear optical polyphos-

phazene polymers containing a sulfonyl-based chromophore have been prepared.101



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Polyphosphazenes containing C60 have also been prepared using macromolecular

substitution of [NLPCl2]n.102

The properties and applications of polyphosphazenes is an area of intense interest.

Polymer electrolytes based on MEEP exhibit very high room temperature ionic

conductivities. Data obtained from vibrational spectroscopy and conductivity

measurements of MEEP containing LiOTf suggested that associated ionic species

play an essential role in charge transport.103 Polyphosphazene nanofibers (mean

diameter ca. 1.2 mm) have been made using electrospinning and were found to

promote the adhesion of bovine coronary artery endothelial cells and osteoblast like

MC3T3-E1 cells.104 Polyphosphazenes containing carboxylic acid substituents have

been prepared and their influence on polymer degradation, microencapsulating

properties and biological activity have been investigated.105 The low temperature

formation of hydroxyapatite–polyphosphazene composites which may be suitable as

bone analogues has been described.106

6 Other main group element-containing polymers

The synthesis and properties of new macromolecular structures composed of main

group elements continue to be explored. This section will describe selected

developments over the past year.

ROMP of organodecaborane-functionalized norbornene or cyclooctene with

Grubbs catalysts affords polymers that are of interest as ceramic precursors.107 An

efficient method for the attachment of Lewis acidic boron centres to the side chains

of organic polymers such as polystyrene has been developed.108 This method has

been utilized to prepare organoboron quinolate polymers (44) that efficiently emit

light at 513–514 nm when excited at 395 nm.109 Blends of polyborazylene and

allylhydridopolycarbosilane in 20 : 80 and 50 : 50 wt.% ratios that were heated to

1000 uC gave SiC–BN ceramic composites.110

Several new developments in the area of Group 15-containing macromolecules

have been made. Particularly noteworthy, was the preparation of analogues of

poly(p-phenylenevinylene) (PPV) where many of the vinylene units (i.e. –HCLCH–)

were replaced by diphosphene (i.e. –PLP–) groups.111 Diphosphene-PPV (46) can be

prepared by irradiating the diphospha-Wittig reagent 45 however the preferred

method involves heating neat 45 to 250 uC for ca. 2 min. Modest molecular weights

of 46 were estimated from GPC analysis (Mn = 5 900; PDI = 2.1) or 1H NMR end

group analysis (Xn = 5.8). The UV/Vis absorption and emission spectra of 46 and

related poly(p-phenylenephosphaaalkene)s prepared in the same study were

consistent with a p-conjugated system. The synthesis and investigation of some

oligomeric model conjugated polymers containing PLP and PLC bonds has been



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reported.112 Phosphaalkene polymer 47 has been prepared and the catalytic activity

of a chelating Pd complex of this macromolecular ligand was examined.113 The

molecular weight (Mn) of 47 was 58 000 g mol21 and the polydispersity was 7.8.

Novel dithienophospholes 48 have been prepared by the 2,2,6,6-tetramethnyl-

piperidinyl (TEMPO) initiated radical copolymerization of phosphole-functionalized

styrene and styrene (ca. 1 : 30 ratio).114 The resultant high molecular weight

copolymer 48 (Mn = 147 650; PDI = 2.46) exhibited a strong blue photoluminescence

in solution (lem = 424 nm) while the corresponding phosphine oxide is red-shifted

slightly (lem = 452 nm).

The addition copolymerization of PLC and CLC bonds has been reported.

Specifically, the radical initiated copolymerization of phosphaalkene 49 and styrene

affords phosphine-containing copolymers 50 (x = 0.05n–0.39n) of moderate

molecular weight (Mw = 3 600–9 000; PDI = 1.4–1.7).115 Interestingly, copolymer

50 shows good activity as a polymer-supported phosphine in the Pd-catalyzed Suzuki

cross-coupling reaction. The ambient temperature anionic oligomerization of 49 in

THF solution has been reported.116 Oligomers 51 with up to 11 repeat units were

detected by using MALDI-TOF mass spectrometry. This provides support that the

polymerization of 49 follows a linear anionic chain grown mechanism similar to that

known for olefins.



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The radical copolymerization of cyclopenta- or cyclohexa-arsines (i.e. 52) with

acetylenes affords poly(vinylene arsine)s 53 (R = aryl or alkyl) of moderate

molecular weight.117–119 The novel arsenic polymers each show fluorescent

properties which has been attributed to the n–p* transition in the main

chain. Fluorescent terpolymers of cyclo-(AsMe)5, phenylacetylene and vinyl

monomers (i.e. styrene, methyl methacrylate) or butadiene monomers have been

prepared and their compositions determined.120 Crosslinked polymers were obtained

if the copolymerization of cyclic arsine and alkyne was performed in the presence

of a diacetylene.121

Analogues of poly(p-phenylene sulfide) containing bis(3,4-ethylenedioxy)-2-

thienyl) spacers have been prepared and possess interesting spectroelectrochemical

properties and moderately high conductivities (1.5 6 1023 S cm21).122

7 Ferrocene-containing and related organometallic polymers

The ROP of suitably strained metalloarenophanes continues to attract attention as a

route to new organometallic polymers. In one such study, the first [1]ruthenoceno-

phanes containing either zirconium or tin (i.e. 54) as the bridging atom were

synthesized and structurally characterized.123 Although no evidence of polymeriza-

tion upon thermolysis was observed for the zirconium compound, the tin-bridged

species 54 was observed to undergo ROP upon heating at 200 uC. The resultant

polyruthenocenylstannane 55 was of high molecular weight (Mw = 2.7 6 105; PDI =

2.28) and exhibited a Tg of 221 uC. Poly(chromarenyldimethylsilane) 57 (a: R = R9 =

Me; b: R = Me, R9 = Et) has been prepared by using platinum-catalyzed ROP of the

corresponding strained silicon-bridged bis(benzene)chromium 56.124 Although

polymer 57a (RLR9LMe) is insoluble in organic solvents, 57b is soluble and the

degree of polymerization was estimated to be ca. 14 by 1H NMR end-group analysis.

A boron-bridged [1]chromoarenophane has been prepared and preliminary

investigations suggest that this compound undergoes ring-opening upon treatment

with BuLi, however no polymers were isolated.125



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1-Sila-3-metallacyclobutane 58 was prepared and was observed to undergo ROP in

THF solution.126 Analysis of 59 (R = Me) by using multi-angle laser light scattering

revealed a bimodal molecular weight distribution with the higher molecular weight

fraction having a weight average molecular weight of 1.75 6 105 g mol21. The

analogous disila polymer 60 was also prepared following a similar ROP strategy.127

Polymer 60 was of moderate molecular weight (Mw = 6 400; PDI = 2.0) and WAXS

analysis suggests that the polymer is partially crystalline. ROMP polymerization of

butadiene-bridged [1]ferrocenophanes has been used to prepare high molecular

weight 61 (Mw > 300 000).128

There were numerous advances in the synthesis and development of ferrocene-

containing polymers in the past year. A major advance was made with the

development of the photolytic living anionic ROP of silicon-bridged [1]ferroceno-

phanes 62.129 Specifically, it was found that treating 62 with Na[C5H4R] (R = H or

Me) gave polyferrocenylsilane 63 with controlled molecular weights and narrow

polydispersities.

The block copolymerization of strained bridged [1]ferrocenophanes (i.e. 62) and

other organic and inorganic monomers continues to attract considerable attention.

For example, PDMS–ferrocenylsilane block copolymers were prepared with



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3-chloropropyl substituents on silicon.130 Nucleophilic substitution at the 3-chloro-

propyl group with DMAP imparted hydrophilic character to the ferrocene block.

These new polymers formed nanoscale vesicular aggregates with diameters of

approximately 85 nm when dissolved in aqueous solution. Polyferrocenylsilane–

polymethylvinylsiloxane copolymers were observed to self-assemble in hexane to

form nanotubes.131 In a study of block copolymers of polyferrocenylsilane and

polyisoprene or polystyrene which self-assemble into ordered states, it was observed

that the disordered state could be stabilized by chemical oxidation of the redox-

active ferrocene units.132 Several other studies of the self-assembly properties of

polyferrocenylsilane block copolymers have been reported.133–135

Several studies of the patterning of ceramic films from the highly metallized

polymer 64 have been reported.136–139 Polyferrocenylsilane-block-polystyrene has

been used as a catalyst precursor for templated carbon nanotube growth.140,141

Polyferrocenes bearing Si, Ge, Sn and P as ferrocene spacers have been found to have

high refractive indices.142 Polymers containing neutral and cationic cyclopentadie-

nyliron groups and azo functionalities within the main chain have been reported.143

8 Polymers containing skeletal d-block elements

As mentioned in the Introduction, the field of coordination polymers has become

such a large field that coordination polymers where the polymeric structure is

retained in solution will be emphasized here. Coordination polymer 65 has been

prepared by treating a diphosphine end-functionalized polytetrahydrofuran (Mn =

7 300; PDI = 1.11) with PdCl2.144 Interestingly, it was found that the molecular

weight of 65 decreased considerably upon sonication. For example, sonication of a

dilute solution of 65 in toluene for 1 h resulted in a decrease in Mw from 1.70 6 105

to 1.02 6 105 g mol21. The reversibility and mechanism of these chain redistribution

reactions were also studied.

Poly-ynes 66 with moderate molecules weights (M = Pt, 14,600; M = Pd, 6 000)

have been prepared and characterized spectroscopically.145 Conjugated polymer 67



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(Mn = 31 700; PDI = 1.9) was prepared and approximately 70% of the phenylene

groups were complexed to chromium.146 Interestingly, cyclic voltammetry suggested

some interaction between the two metal centres via the conjugated bridge in the

polymer chain.

The condensation of Pd2(dmb)2Cl2 (dmb = 1,8-diisocyano-p-menthane) and

various bis(diphenylphosphines) with butane, pentane, hexane and acetylene

spacers in the presence of LiClO4 affords polymers of the form {[Pd2(dmb)2-

(diphos)](ClO4)2}n.147 In solution, the polymers were found to consist of 12 to 16

repeat units and were strongly luminescent in PrCN glasses at 77 K. Similar

polymers to the palladium polymers that were just described have been prepared and

characterized with copper and silver atoms in place of palladium.148

Novel gold(I) polymers have been prepared and characterized in the solid state by

X-ray crystallography.149 Unfortunately, the polymers were insufficiently soluble for

solution characterization. One dimensional coordination polymers have been

prepared with Ag–Pd metal–metal bonds in the main chain.150

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22 inorganic and organometallic polymers

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