23??inorganic and organometallic polymers

23 Inorganic and organometallic polymers

Derek P. Gates

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

There were numerous advances of particular significance to the field of inorganicpolymer science reported in 2002. In the main group, highlights include the observ-ation of the abrupt conformational changes in polysilane monolayers and the prepar-ation of conjugated polymers containing phosphorus and arsenic. Highlights in thearea of metal-containing polymers include the preparation of spherical magneticceramics from polyferrocenylsilane microspheres and the direct observation of thering-opening polymerisation of novel strained gold() macrocycles.

1 Introduction

Research in the broad field of inorganic polymer chemistry continued to flourish in2002. The development of polymers composed of main group elements or transitionmetals attracts interest from researchers in main group, organometallic, polymer, andmaterials chemistry. Researchers are motivated by the challenges associated withdeveloping new synthetic methodologies and the prospect of finding materialspossessing unusual properties and thus possible speciality applications.

This article will review the highlights in the field of inorganic and organometallicpolymer science during the year 2002. The format of this review will follow in thetradition established in the previous articles of this series,1–5 and is comprised of threesub-sections. The first two sections discuss aspects of the chemistry of main group-element-containing polymers, whilst the last provides an overview of recent develop-ments in d-block element-containing macromolecules. In this article emphasis isplaced on the synthesis and study of linear polymers possessing inorganic elementswithin the main chain. However, in some instances novel polymers with inorganicelements in the side-group structure or dendritic materials containing inorganicelements will also be highlighted.

A number of reviews and highlights in the area of inorganic polymer chemistryhave appeared over the past year. There is an interesting report outlining the varioussynthetic routes to silicon carbide materials.6 This review includes an excellent over-view of the synthetic approaches to polysilanes and polycarbosilanes used as pre-cursors to SiC ceramics. The preparation and property evaluation of isolated singlepolysilane chains has been outlined by Furukawa.7 A review of the utility of silyl

DOI: 10.1039/b211500j Annu. Rep. Prog. Chem., Sect. A, 2003, 99, 453–466 453

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triflate intermediates in the synthesis of organosilicon polymers [e.g. poly(silylene-methylenes), polysilanes, polysilynes, poly(silylenealkynes), etc.] and their function-alisation and cross-linking has been published.8

The recent development of some new phosphorus-containing macromolecules hasbeen overviewed by Manners and co-workers.9 Several reviews in the area of phos-phorus-containing dendrimer chemistry have appeared.10–12 An interesting mini-review has been published which deals with the optical properties of molecular andpolymeric systems containing boron.13

A number of reviews have been published in the area of transition metal-containingpolymers. Macromolecular systems containing metal complexes with bipyridine andterpyridine ligands have been reviewed by Schubert and Eschbaumer.14 Many novelpolymer systems with metal complexes in the polymer side-chain and dendrimerscontaining transition metals are described. Abd-El-Aziz has written a comprehensivereview of organometallic polymers in which he describes the synthesis of macro-molecules with metals in the main chain and side-group structure.15 Bera and Dunbarhave provided an interesting highlight of one-dimensional materials composed oftransition metals in the backbone.16 In addition, several other reviews outlining recentdevelopments in metal-containing polymer science have appeared over the pastyear.17–21

2 Group 14 element-containing polymers: polysiloxanes (silicones),polysilanes, and others

The mature field of polysiloxanes has continued to attract significant attention.An improved method for the efficient preparation and purification of cyclic poly-(dimethylsiloxane) (PDMS) 2 has been developed.22 The procedure begins with thedeprotonation of a commercially available linear precursor 1 (Mn ∼ 2460 g mol�1)followed by the addition of a dilute solution of dichlorodimethylsilane. The linearanionic polymer was then separated from the cyclic polymer 2 using an anion-exchange resin. The polysiloxane 2 was characterised by NMR and IR spectroscopy,GPC and MALDI-TOF MS which were consistent with the assigned cyclic structure.

The anionic ring-opening polymerisation (ROP) of hexavinylcyclotrisiloxane (3) toyield poly(divinylsiloxane) 4 (Mn = 4.0 × 104 g mol�1; PDI = 1.28), a new functionalpolysiloxane, has been reported by Cai and Weber.23 Interestingly, the glass transitiontemperature (Tg) for 4 (�134 �C) is lower than that for PDMS (�123 �C). The vinylsubstituents of 4 could be hydrosilylated with RMe2SiH (R = fluoroalkyl) andKarstedt’s catalyst giving 5. Both the products of anti-Markovnikov (major) andMarkovnikov (minor) hydrosilylation are observed. In a separate study, the anti-

454 Annu. Rep. Prog. Chem., Sect. A, 2003, 99, 453–466

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Markovnikov addition of 9-acetylphenanthrene to poly(vinylmethylsiloxane) hasbeen accomplished using ruthenium catalysis.24 This new fluorescent polymer has ahigh Tg (88 �C) which has been attributed to the planar nature of the phenanthreneunits which affects the flexibility of the siloxane backbone. The synthesis and fluor-escent properties of a pyrene end-functionalised PDMS have been investigated.25

The mechanism of the cationic polymerisation of 2,2-diphenyl-4,4,6,6-tetramethyl-cyclotrisiloxane initiated by triflic acid has been studied using 29Si NMR at the pentadlevel and statistical methods.26 The results suggested that monomer addition givingsymmetrical siloxane –OSiMe2–OSiPh2–OSiMe2– (68%) and unsymmetrical siloxane–OSiMe2–OSiMe2–OSiPh2– (32%) units dominated the chain growth process. Inter-molecular exchange of chain fragments and backbiting processes, which would lead toan irregular polymer structure, appear to be minimal. The polymerisation of octa-methylcyclotetrasiloxane using bis(trifluoromethane)sulfonimide as an initiator and(Me3Si)2O as a chain end blocker was used to prepare low molecular weight α,ω-bis-(trimethylsilyl)-poly(dimethylsiloxane) (Mn < 1.3 × 104 g mol�1).27

The hydrosilylation polymerisation of siloxy ketone (6) using in situ generated“Ru(CO)(PPh3)2” as a catalyst yields an unsymmetrical poly(silyl ether) (7).28 Simi-larly, a α,ω-diketone and a α,ω-dihydridooligodimethylsiloxane were copolymerisedwith the same ruthenium catalyst to give a symmetrical poly(silyl ether) with molecu-lar weights of ca. 104 g mol�1. The polymers were characterized by 1H, 13C and 29SiNMR spectroscopy and their thermal properties evaluated using TGA and DSC. Theanionic ring-opening polymerisation (ROP) of strained 1-oxa-2,5-disilacyclopentaneshas been reported.29

Molecular dynamics simulations have been used to study the structure of liquidPDMS and the results were found to be in good agreement with data obtained usingwide-angle X-ray scattering.30 The chain dynamics of PDMS in its inclusion com-pound with γ-cyclodextrin were studied using fast-MAS solid-state NMR spectro-scopy.31 The segmental relaxation near the glass transition (α-relaxation) was studiedin end-linked PDMS networks and poly(methytolylsiloxane).32,33 Time-resolved fluor-escence was used to study the dynamics of linear poly(methylphenylsiloxane).34 Theformation of PDMS gels by end-linking vinyl terminated silicones to silanes throughhydrosilylation has been studied using FTIR and GPC.35

Annu. Rep. Prog. Chem., Sect. A, 2003, 99, 453–466 455

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Block copolymers of poly(dimethylsiloxane) and polystyrene of moderate molecu-lar weight (ca. 104 g mol�1) have been prepared by combined anionic ROP andnitroxide-mediated radical polymerisation.36 Several polyorganofluorosiloxane-block-polyimide block copolymers were prepared and their thermomechanical, dynamicmechanical and water repellency properties investigated.37 The adhesive properties ofpoly(imidesiloxane) copolymers containing multiple siloxane segment lengths wasinvestigated.38 The mobility, structure and domain size in polyimide-poly(dimethyl-siloxane) networks was investigated by using solid-state 29Si, 13C and 1H NMRspectroscopy.39

Kawakami and co-workers have prepared novel optically active hyperbranchedpoly(carbosiloxanes) from the platinum-catalysed hydrosilylation copolymerisation ofchiral trisiloxane 8 and achiral disiloxane 9.40 The polymers had molecular weights ofup to 9 × 103 g mol�1 and the degree of branching was estimated from analysis of the29Si NMR spectra.

The development of polymers containing silsesquioxanes received significant atten-tion over the past year.41,42 Novel crosslinked polysiloxanes 10 (X = η5–C5H5, O

iPr;simplified structure) were prepared from vinyl titanium silsesquioxane and methyl-hydrosiloxane dimethylsiloxane copolymers using platinum catalysed hydrosilyl-ation.43 The heterogeneous three-dimensional network polymers 10 are effectivecatalysts for the epoxidation of cyclooctene with H2O2.

The development of polymers containing catenated silicon atoms in the backbonecontinues to attract considerable interest due to the novel properties of thesematerials. There are several studies of the helical nature of the polysilane backbone.Sato and co-workers have studied the torsional fluctuation and helix reversal of optic-ally active polysilanes 11 and 12.44 The helical screw-sense inversion in random poly-silane copolymers consisting of varying ratios of chiral and achiral monomer units


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has been investigated.45 Preferential helical screw-senses were observed for achiralpolysilanes 13 and 14 when dissolved in optically active solvents.46 Interesting liquidcrystalline phases were observed for the rigid-rod helical polysilanes 15 of varyingmolecular weights.47 Interestingly, a Grandjean texture with oily streaks, indicative ofa cholesteric phase, was observed (Mw = 1.04 × 104; PDI = 1.16) at 100 �C; whilst formore monodisperse samples (Mw = 1.93 × 104; PDI = 1.11), a fan-shaped Smectic Atexture was obtained at 100 �C.

An interesting study of the conformational behaviour of thin films of polysilaneshas been conducted by Nagano and Seki.48 Specifically, when a single monolayer ofpoly(dihexylsilane) is formed using a liquid crystalline layer of 4�-pentyl-4-cyano-biphenyl on water only the helical-gauche conformation (λmax = 320 nm) was observed,rather than the all-trans-zigzag conformer (λmax = 370 nm) of the bulk state. Remark-ably, as multiple layers of polysilane were built up, an abrupt change in the UV/Visibleprofile was observed at the sixth layer (ca. 8 nm thick). The all-trans-zigzag andhelical-gauche conformations were both observed, suggesting that when poly(di-hexylsilane) chains are placed at distances 8 nm away from the surface the polymersegments can freely aggregate into their thermodynamically preferred state.

Furukawa and co-workers have described a novel strategy to synthesise “sulfidetripod” terminated polysilanes 18 from the living anionic polymerisation of maskeddisilene 16 and quenching the living polymer 17 with a sulfur-containing bromo-alkane.49 The resulting polymers were chemisorbed onto gold surfaces and studiedusing AFM and UV absorption. In a separate study, poly(dihexylsilane) end-graftedonto a quartz surface showed temperature dependent electronic absorption spectrasimilar to poly(dihexylsilane) in dilute solution.50


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Dehydrocoupling has been used to prepare polysilole 19 with moderate molecularweights (Mw ∼ 4000–6000 g mol�1) and in high yields (77–88%).51 Silanes with carb-osilyl substituents were polymerised using dehydrocoupling with Cp2TiCl2–BuLi andthe tacticity of the resultant polysilanes was probed using 29Si NMR spectroscopy.52

Variable-temperature UV-Visible and Raman spectroscopies were used to detect athermochromic phase transition which occurs on cooling poly(di-n-butylstannane)over the temperature range 260–200 K.53 These studies revealed that the transitioninvolves transformation from a disordered polymer backbone to a more ordered con-formation (possibly, all-anti or transoid). A new mechanism has been proposed for themetal-catalyzed dehydrocoupling of stannanes.54 There is evidence from NMR studiesthat free stannylene (Mes2Sn:) inserts into an Sn–H bond of Mes2SnH2 formingMes2HSn–SnHMes2.

Poly(silylenemethylene)s with mesogens in the side-chain structure have been pre-pared and characterised by X-ray diffraction, DSC, TEM, and polarizing opticalmicroscopy.55,56 The novel polymers show highly ordered smectic liquid crystallinephases. Photoluminescent oligocarbosilanes 20 were prepared by the platinum-catalysed hydrosilylation polymerisation of PhC��CSiMe2H.57 Similarly, hydrosilyl-ation was used to prepare hyperbranched σ–π-conjugated polymers from (HC��CAr)2-MeSiH.58 The living anionic copolymerisation of dialkylsilacyclobutanes 21 (R = Me,Et, Bu) with methacrylic esters to yield amphiphilic diblock copolymers 22[m = 10–26, n = 20–38; PDI = 1.13–1.28] has been reported.59 These interestingmacromolecules self-assemble in methanol to give micelles or at water surfaces to givemonolayers.

Acyclic diene metathesis (ADMET) polymerisation of chlorosilanes 23 usingSchrock’s catalyst gives a functional polycarbosilane 24 that reacts with alkyl- or aryl-lithium reagents in a macromolecular substitution reaction yielding 25.60 The prepar-ation of carbosilane dendrimers with (perfluoroaryl)boranes or platinum complexeson the periphery have been reported.61,62


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3 Group 15 element-containing polymers: polyphosphazenes, andother main group element-containing macromolecules

The development of new polyphosphazenes as proton conductive polymer mem-branes for application in fuel cells continues to attract considerable interest. Allcock etal. have reported the development of polyphosphazenes bearing phenylphosphonicacid side groups.63,64 Macromolecular substitution of polydichlorophosphazenewas used to prepare mixed substituent polyphosphazenes 26 with sulfonamide sidegroups which showed good proton conductivity.65 Membranes constructed of pro-tective layers of poly[bis(methoxyethoxyethoxy)phosphazene] (MEEP) and poly-phosphazene 27 on lithium metal were studied as anodes for lithium fuel cells.66

Polyphosphazenes containing oxypyridine substituents and their complexes withW(CO)5(HOMe) have been reported.67 Similarly, interesting high molecular weightpolyphosphazenes 28 with pendant phosphine complexes [Mw = 1.1 × 106; PDI = 4]have been prepared.68 Interestingly, these new manganese-containing polymersshowed a glass transition (Tg = 128 �C) and were remarkably stable, remainingunchanged in the solid-state for years. An improved route to non-linear opticalpolyphosphazenes containing indole-based chromophores has been developed.69

Polyphosphazene hydrogels have been reported that form clear solutions and becomeviscous at 11 �C and gel at 38 �C, but begin to shrink above that temperature.70 Thissol–gel process was reversible and shows no hysteresis. Biodegradable non-toxicpolyphosphazenes have been prepared which degrade in phosphate buffered salineover approximately one month.71

A new high yield synthesis of Cl3P��NSiMe3, a monomer for the preparation ofcontrolled molecular weight polyphosphazene homopolymers and block copolymers,has been reported.72 Amphiphilic biodegradable block copolymers, poly[bis(ethylglycinat-N-yl)phosphazene]-block-poly(ethylene oxide), have been prepared using theambient temperature cationic polymerisation of Cl3P��NSiMe3.

73 The synthesis andmicellar characteristics of poly[bis(trifluoroethoxy)phosphazene]-block-poly(ethyleneoxide) have been investigated.74 TEM and dynamic light scattering studies suggest thatspherical micellar aggregates with average diameters of 100–120 nm are formed.


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Currently, there is considerable interest in the preparation of polymers containingGroup 15 elements that possess interesting electronic properties. Gates et al. havereported the first examples of π-conjugated P��C-containing analogues of poly-(p-phenylenevinylene) using a condensation polymerisation strategy.75 Yellow poly-(p-phenylenephosphaalkene) 29 of moderate molecular weight [Mn = 103–104 g mol�1]is the first polymer with low-coordinate phosphorus atoms in the main chain. Theelectronic properties of moderate molecular weight poly(p-phenylene-P-alkyl-phosphines) 30 and related systems, prepared using a palladium or nickel medi-ated coupling route, were investigated.76 The first examples of a soluble polymercontaining arsenic atoms in the main chain has been prepared by Naka, Chujo andco-workers. The novel poly(vinylene-arsine)s 31 (R = Me, Ph) were prepared byradical copolymerisation of “RAs”, generated from pentamethylcyclopentaarsine,and phenylacetylene.77

A series of phosphorus-containing dendrimers having chiral ferrocenic subunitshave been prepared and their electrochemical properties were found to be dependenton the depth of the sub-shell where the units were placed.78 In contrast, the chiro-optical properties were not affected by where the units were located within thedendrimer.

Jäkle and co-workers have reported the synthesis of highly Lewis acidic perfluoro-arylborane-containing side-chain polymers through a post-polymerisation modifi-cation of poly(4-trimethylsilylstyrene) with BBr3.

79 Rigid-rod poly(cyclodiborazane)scontaining metallayne moieties in the main have been prepared.80 Ion conductivemacromolecules containing mesitylborane or mesitylborate units and oligo(ethyleneoxide) functionalities in the main chain were prepared using hydroboration ordehydrocoupling strategies.81

4 Polymers containing skeletal d-block elements

The development of synthetic methodologies to incorporate transition metals directlyinto the main chain of linear macromolecules continues to attract considerableinterest. In this context, ferrocene-containing polymers remain the most widelyinvestigated. In the past year, a new route to moderate molecular weight soluble poly-ferrocenylenes from the Ullmann coupling of diiodoferrocenes was reported.82 Severalwater-soluble polymeric electrolytes derived from macromolecular substitution ofchlorosilane functionalised polyferrocenylsilanes or the ROP of stubstitutionallylabile of silicon-bridged [1]ferrocenophanes was reported.83 Anionic polyelectrolyteswere prepared by side-group modification of polyferrocenylmethylchloropropyl-silanes through substitution with methylmalonate species.84 The layer-by-layer self-assembly of multilayers of anionic/cationic polyferrocenylsilanes has been achieved.85


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Iodine-doping of polyferrocenylsilane or germane thin films produced materialswith conductivities of 10�4–10�7 S�cm�1 compared with undoped conductivities of ca.10�14 S cm�1.86 The platinum-catalysed ROP of [1]ferrocenophanes bearing acetylenicsubstituents produced soluble high molecular weight (Mn>104–105 g mol�1) polymersthat gave excellent ceramic yields upon thermolysis.87

Rhodium() complexes [Rh(1,5-COD)2]OTf, [Rh(1,5-COD)2]PF6 and [Rh(1,5-COD)(dmpe)]OTf were found to be effective catalysts for the ROP of strained silicon-bridged [1]ferrocenophanes and disilacyclobutanes.88 Interestingly, prolongedexposure of the polymer to the [Rh(1,5-COD)2]X catalysts resulted in polymer deg-radation whilst exposure to the phosphine catalyst did not result in decomposition.Studies of molecular models suggested that Cp–Si bond cleavage was the major modeof decomposition.

The “spontaneous” ambient temperature polymerisation of tin-bridged [1]ferro-cenophanes has been investigated by Manners and co-workers.89 Reactions of themonomer 32 with radicals and radical traps, neutral and anionic nucleophiles, Lewisacids, protic species and other cationic electrophiles led to the discovery of two newROP mechanisms for [1]ferrocenophanes. Specifically, the addition of nucleophilicamines such as pyridine, or electrophilic species H� and Bu3Sn�, to solutions of 32were found to dramatically accelerate the formation of 33 at ambient temperature.This result suggests that the “spontaneous” polymerisation of 32 may be caused bytraces of acidic or basic impurities.

In 2002 there continued to be a significant amount of work published on the syn-thesis and properties of block copolymers containing polyferrocenylsilane blocks.90–94

In one study, TEM micrographs showed that poly(ferrocenylsilane-siloxane) blockcopolymers with block ratios of 1 : 12 form nanotubes of up to 0.1 mm in length whenformed from non-polar hydrocarbon solvents.90 Novel ABC triblock copolymers 34with narrow polydispersities (1.04–1.06) were prepared using living anionic ROP andformed self-assembled cylindrical or spherical micelles depending on the length of theA block.91

Shaped magnetic ceramics composed of 15–700 Å α-Fe particles dispersed in a SiC/C/Si3N4 matrix were prepared from the pyrolysis of cross-linked polyferrocenylsilanenetworks 36.95 Stöver, Ozin, Manners and co-workers have reported full details of the


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preparation and study of novel polyferrocenylsilane microspheres.96 The platinum-catalysed copolymerisation of equimolar ratios of dimethylsilicon-bridged [1]ferro-cenophane and cross-linked 35 in poor solvents for the polymer gave cross-linkednetworks which precipitated as microspheres. The pyrolysis of the microspheresbetween 600 and 900 �C gave spherical ceramic particles (average diameters 1.7–2.2µm) that displayed magnetic ordering in an external magnetic field.

The polycondensation of a doubly silyl-bridged cyclopentadienyl anion with sol-vated MX2 (M = Fe, Ni, Cr) resulted in the formation of both linear chains andrings.97 For iron, MALDI-TOF MS analysis showed that, depending upon the condi-tion of polymerisation, rings containing 6–12 ferrocene moieties and chains of 2–12repeat groups were formed. Jutzi and co-workers reported the molecular structures ofthe first 1,1�-digallylferrocene linear solid-state polymers.98 Pentaphosphaferrocene[Cp*Fe(η5–P5)] has been used as a linking unit in the preparation of novel one- andtwo-dimensional copper polymers.99

An interesting series of cyclopentadienyliron-complexed azo-functionalised poly-mers were reported by Abd-El-Aziz, et al.100 Novel ferrocene-containing macromole-cules, such as 37, were prepared by condensation polymerisation and their redoxproperties were examined using cyclic voltammetry.101 The CV showed two isolatedredox waves. Therefore, it was concluded that there was no electrochemical communi-cation between the iron centres in the polymer.

Upon treatment with 4,4�-bipyridine the novel zinc-porphyrin polymer 38 formed adouble-strand conjugated ladder polymer 382�(Bipy)n.

102 The double-strand polymer382�(Bipy)n showed significantly enhanced optical nonlinearity when compared withanalogous single-strand polymers. A novel sensor for nitric oxide has been developedbased on the cobalt salen polymer 39.103

Conjugated poly(aryleneethynylenes) containing 2,2�-bipyridine groups in the mainchain have been complexed to ruthenium bipyridyl moieties to yield novel metal-containing polymers.104 Acetylide functionalised oligopyridines and thienyl-pyridineshave been used to prepare functional platinum poly-ynes.105,106 Interesting coordin-ation polymers with sinusoidal backbones have been prepared from the reactions of


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the rigid ligand 1,2-bis(3-pyridyl)ethyne and Cd(), Co() and Cu() salts.107 Poly-(p-phenyleneethynylene) derivatives complexed to Pt(0) through the alkyne moietieswere shown to have the highest charge carrier mobilities yet observed in disorderedconjugated networks.108

Electropolymerisation of thiophene-substituted terpyridine complexes ofruthenium has been used to prepare polymers containing [Ru(terpy)2] groups in thebackbone.109 Copper()-containing coordination polymers of up to 47 repeat unitshave been prepared from the reaction of Cu(OTf )2 and bis(2,2�-bipyrid-6�-yl)-ketone.110 A novel one-dimensional macromolecule composed of Cu2(O2CMe)2 as adimetallic spacer linked by 1,3-di-4-pyridylpropane groups has been assembled andcharacterised crystallographically.111 An interesting polymer 40 composed of a back-bone of alternating short [2.771(5) Å] and long [2.849(5) Å] bismuth-iron distanceshas been characterised crystallographically.112

Puddephatt and co-workers have studied the ROP of the macrocyclic gold complex41 to form a novel helical polymer 42.113 Complex 42 was characterised in the solid-state by X-ray diffraction, however, remarkably equilibrates to the ring structure 41 insolution. Enthalpy effects strongly favour the polymer 42, whilst entropy effectsstrongly favour the ring 41. The preparation of the first neutral polymer with lineargold() centres bridged by dithiolate and diphosphine ligands has been reported.114


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An acrylate functionalised core of two iron() centres complexed by pyridylimineligands was copolymerised with methyl methacrylate to give fascinating triple-helicalpolymers.115 Hydrogen bonding between amide groups has been used to construct adouble-helical organometallic macromolecule containing octahedral platinum()centres in the main chain.116

There continues to be significant interest in the development of dendritic materialscontaining transition metals.117–123,124 Metallocene dendrimers containing 64 19-electron iron() centres on the surface have been shown to reduce C60 to its mono-anion.117 Dendrimers containing palladium complexes have been developedby van Koten, et al. as supports for Lewis acid catalysed aldol condensationreactions.120 A novel approach to the synthesis of π-delocalised organometallicdendrimers containing bis(acetylide) complexes of the Ru(dppe)2 building block hasbeen developed.122 Bunz and co-workers have synthesised novel organometallicpolyphenylene dendrimers centred upon a cyclobutadienecyclopentadienylcobaltmoiety.124

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23??inorganic and organometallic polymers

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