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METAL-CONTAINING POLYMERS

Introduction

The development of organometallic chemistry in the 1950s has played animportant role in the redefinition of polymer chemistry. While organic andinorganic polymers (qv) were previously the only two classes of macromolecules,the introduction of metals into polymers marked the beginning of a new field ofresearch (see INORGANIC POLYMERS). The combination of polymeric and metallicproperties has caused a surging interest in the development of metal-containingpolymers over the past few decades (1–5). It is well known that depending onthe elements and the types of bonding present, the properties of these polymersdiffer dramatically. The degree of polymerization and the nature of the metal alsohave strong influences on the properties of polymeric materials. It is the diversearray of electrical, electrochemical, magnetic, optical, and catalytic propertiesthat define the applications of metal-containing polymers.

In recent years, many reviews have been dedicated to advances in the field ofmetal-containing polymers (6–14). Although this article classifies these polymersaccording to their structures, many of these polymers could have been includedin more than one section. The aim of this work is to give an overview of thesynthesis, properties, and applications of metal-containing polymers, with a focuson the developments that have taken place over the past two decades.

Metals in Polymer Backbones, σ-Bonded Systems

Polymers with metals σ -bonded to organic spacers in their backbones have beenstudied in recent years because of their electrical and optical properties (14,15).This class of organometallic polymers can be prepared via reactions occurring

1Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

2 METAL-CONTAINING POLYMERS Vol. 7

at the metal center or at the ligand sites. Nickel complexes with bromo sub-stituents (2) react with lithiated aromatic compounds (1) to yield the correspond-ing organonickel polymers (3) (eq. 1). The solubility of these polymers is low, andanalysis of 3 indicates that their degree of polymerization is between 8 and 13 (16).

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Many different transition metals have been incorporated into polymers con-taining C C triple bonds in order to enhance metal dπ–pπ∗ back bonding, whichis expected to contribute to π -electron delocalization (17–30). Although much ofthe research on organometallic acetylide polymers has dealt with Group 10 transi-tion metals, the synthesis of acetylide polymers containing Ni (17), Pd (17–19), Pt(17,20–23), Fe (24,25), Ru (25,26), Os (25), Rh (23,27), Au (28,29), and Zr (30) hasbeen reported. The incorporation of metals into polyynes generally results in mate-rials with band gaps ranging from 2.4 to 3.2 eV, which is higher than that of manyorganic materials (<1 eV) (20). Lewis and co-workers demonstrated that incorpo-rating alternating electron donor and acceptor groups into platinum acetylidepolymers resulted in materials with band gaps below 2 eV (20). Equation 3shows the synthesis of a rigid-rod iron acetylide polymer prepared via the reac-tion of a dichloro complex of iron (4) with a bistrimethylstannyl acetylide monomer(5), resulting in the formation of a conjugated polymer (6) with a weight averagemolecular weight of 173,000 (25).

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Reaction of terminal al kynes (7) with transition metal halides (8) in thepresence of KOH has been used in the synthesis of gold-containing polymers (9)(28,29). It was found that the solubility of these polymers could be controlledthrough the choice of phosphine ligands at the gold centers.

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Vol. 7 METAL-CONTAINING POLYMERS 3

Oligomeric complexes containing metals σ -bonded and π -coordinated to or-ganic groups have been prepared via palladium-catalyzed coupling reactions (24).The synthesis of zirconocene acetylene polymers (12) has been reported via thereaction (eq. 4) of bis(pentamethylcyclopentadienyl) zirconium(IV) dichloride (10)with dilithioacetylene or dilithiodiacetylene (11) R = C C or C C C C (30).These polymers displayed poor solubility in organic solvents other than n-hexane,and their weight average molecular weights ranged from 55,000 to 68,000.

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In 1973, the synthesis of titanium, zirconium, and hafnium polyesters via reactionof the dicyclopentadienylmetal dichloride complexes with disodium dicarboxylatesin either aqueous or organic solvents was reported (31). Around the same time thesynthesis of polyethers and amines of titanocene and polythioethers of zirconocenewas also reported using similar methodologies (32,33).

Tilley and co-workers have reported the synthesis of polymers containing zir-conacyclopentadiene rings in their backbones (34,35) (eq. 5). The zirconacyclopen-tadiene units were subsequently converted into organic functionalities whilemaintaining the integrity of the polymers. The synthesis of polymers containingcobaltacyclopentadiene groups within their backbones has also been investigated(36–39).

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Polymers with Metal–Metal Bonds

Polymers with M M bonds represent a relatively unexplored area of organometal-lic polymer chemistry. This is in part due to the instability of M M bonds; however,such classes of photoreactive polymers are important in the design of degrad-able plastics and medical supplies as well as lithographic materials. Tyler and


co-workers have developed photochemically reactive polymers (18) via condensa-tion reactions of monomers containing Fe Fe or Mo Mo bonds (16) with organicmonomers such as diisocyanates (17) (40–43) (eq. 6). The resulting polymers couldbe photolyzed, resulting in cleavage of the metal–metal bonds.

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Cuadrado and co-workers have prepared a polymer with Fe Fe bonds inits structure (19) via reaction of a polysiloxane with Fe(CO)5 (44). The insolublenature of this polymer indicated that cross-linking between polysiloxane chainsoccurred upon formation of the organoiron polymer. Silicon polymers containingCo Co bonds (20) have been prepared via the reaction of Co2(CO)8 with the triplebonds of a silicon based polymer (45). Mixed metal systems were also describedin which complexes containing arenes coordinated to chromium tricarbonyl werereacted with Mo2Cp2(CO)6 or Co2(CO)8.

Polymeric materials containing Pt Pt bonds in their backbones have beenexamined (46). The formation of platinum polymers (23) was achieved via reactionof the platinum complex (21) with diacetylides, diphosphines, or diisocyanides (22)(eq. 7).

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Polymers whose backbones consisted solely of metal–metal bonds have beensynthesized by electrochemical reduction of ruthenium and osmium complexes(47,48). Reduction of [MII(trans-Cl2)(bipy)(CO)2] (M = Ru, Os) (24) to M0 com-plexes generated a polymeric film (25) following loss of the trans chloride ligands(48) (eq. 8). Both the ruthenium- and osmium-based coordination polymers wereselective for the reduction of carbon dioxide.

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Polymers containing metal–metal single (26) and multiple bonds (27) havealso been prepared via reaction of bimetallic carboxylates with coordinating lig-ands (49–53). It has been found that polymeric materials containing Mo Mo triplebonds crystallize from solutions of Mo2(O2CCH3)4 in bidentate ligands such as1,2-bis(dimethylphosphino)ethane or tetramethylenediamine (53).

π-Coordinated Systems, Metallocene-Based Systems

Polymerization of ferrocene derivatives marked the beginning of a new erain polymer chemistry (54). In the early 1960s, Korshak and Nesmeyanov re-ported the synthesis of ferrocene-based polymers by reacting ferrocene withtert-butyl hydroperoxide (55,56). Neuse later reported that these polymers con-sisted of homoannular and heteroannular aliphatic ether-substituted units withnumber-average molecular weights less than 7000 (57). Methodologies usingmetal salts have also been implemented in the synthesis of polyferrocenylenes;however, these polymers had ambiguous structures and low molecular weights(58,59). The reaction of dihaloferrocenes with magnesium resulted in polyfer-rocenylenes with conductivities ranging from 10− 2 to 10− 4 S/cm (60–62). Theconductivity of this crystalline polymer was higher than the conductivity of amor-phous polyferrocenylene. In 1996, Nishihara and co-workers synthesized a soluble1,1′-dihexylferrocene-based polymer and its electrochemical properties and pho-toconductivity were examined (63).


The synthesis and polymerization of a mercuriferrocene complex was re-ported in 1963 (64). Decomposition of this polymer gave 1,1′-diiodoferrocene or1,1′-ferrocenedicarboxylic acid along with other products. It was later reportedthat poly(mercuriferrocenylene) could be converted to polyferrocenylene by react-ing the poly(mercuriferrocenylene) with ferrocene at 245–260◦C (65). Polymersprepared via reaction of ferrocenes functionalized with carboxylic acids, acid chlo-rides, alcohols, and amines have been utilized to synthesize condensation polymerscontaining ferrocenyl units in their backbones (54,66–69). In 1984, Rausch andco-workers reported the synthesis of polyamides and polyureas from the reactionof 1,1′-bis(β-aminoethyl)ferrocene (28) with diisocyanates (29) or diacid chlorides(30) (66) (eq. 9).

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More recently, a soluble polymer (32) was prepared via reaction of1,1′-ferrocenedimethanol with 4,4′-biphenyltetraamine in the presence of[RuCl2(P(C6H5)3)3] (70). Approximately 20% of the iron centers were found tobe in the Fe(III) state as a result of oxidation by ruthenium complexes formedduring the polycondensation reaction. Wright and co-workers have reported thesynthesis of ferrocene-based polymers possessing nonlinear optical properties (33)(71–73). These polymers were formed by polycondensation of a difunctionalizedferrocene monomer (71).

Like their isoelectronic ferrocene counterparts, cobaltocenium units are re-sistant to strong oxidizing agents and possess interesting electrochemical be-havior. The synthesis of polyesters and polyamides containing cationic cobaltunits in the main chain has been reported (32,74–76). Sheats and Carraher re-ported the synthesis of cobaltocenium polymers containing tin, antimony, tita-nium, and zirconium atoms in their backbone via the reaction of the dicarboxylic


acid complex of cobaltocenium with the corresponding organometallic monomers(32,75). Cuadrado and co-workers prepared polyamides containing siloxanebridges (36) via condensation of 1,1′-bis(chlorocarbonyl)cobaltocenium hexaflu-orophosphate (34) with a siloxane-based diamine (35) (76) (eq. 10). This polymerdisplayed very limited solubility in polar organic solvents; however, the analogousferrocene-based polymer had an Mn value of 10,600 (77). These ferrocene-basedpolymers were utilized in the production of chemically modified electrodes.

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The synthesis of conjugated polymers containing ferrocene units in theirbackbones has received much attention in recent years (78–81). Bochmannand co-workers have described the synthesis of ferrocene-based polymers viapalladium-catalyzed coupling reactions of dihalide or divinyl functionalized fer-rocene monomers with aromatic spacers (37) (78).

Conjugated polymers have also been prepared via reaction of dilithiobis(3-hexyl-4-methylcyclopentadienide)arylenes (38) with ferrous iodide (82). Us-ing a similar strategy, poly(ferrocenylsilane) was prepared by reaction of thedilithium salt of dicyclopentadienyldimethylsilane (38, R = Si(CH3)2, R′, R′′ =H) with ferrous chloride (83) (eq. 11).

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Reaction of 1,1′-ferrocenedithiol with diarylsilanes resulted in the forma-tion of polymers containing sulfur–silicon bonds between the ferrocenyl units(84). These organometallic polymers exhibited good air and moisture stability.Ferrocene polymers containing disulfide linkages (42) have been synthesized byring-opening polymerization (ROP) and desulfurization of [3]-trithiaferrocenenes(41) (85–87) (eq. 12). High molecular weight linear and network poly(ferrocenepersulfides) were produced by reaction of the trithiaferrocenenes with P(C4H9)3.

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The ROP of [1]thia- and [1]selenaferrocenophanes has been accomplishedthermally and in the presence of anionic initiators; however, the resultingpolymers were insoluble (88). Methylation of the cyclopentadienyl rings ofthe [1]thiaferrocenophane, followed by ROP, allowed for the isolation of solu-ble poly(ferrocenyl sulfide). The cyclic voltammograms of these materials in-dicated the presence of two reversible oxidation processes, and it was foundthat these polymers possessed stronger Fe Fe interactions than the analogoussilicon-bridged materials (88). Polyferrocenes containing sulfide linkages werealso prepared via thermal and cationic ROP of [2]carbathioferrocenophane (89).

Metallocenophanes containing hydrocarbon bridges have been polymerizedthermally to give polymers containing insulating bridges between the cyclopen-tadienyl ligands (90–92) (eq. 13). It was found that if the R group in 43 washydrogen, the resulting polymers were insoluble, whereas isomeric mixtures of43 (R = CH3) resulted in soluble polymetallocenes (44). Cyclic voltammetry ofthe poly(ruthenocenylethylenes) showed irreversible oxidation processes at 0.60V, while poly(ferrocenylethylenes) underwent reversible oxidation processes at−0.27 V (92).

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Ring-opening metathesis polymerization (ROMP) of ferrocenophanes con-taining bridging olefinic groups (45, 46 48) has been examined in order to syn-thesize conjugated ferrocene-based polymers (93–95). The polymers synthesized


from ROMP of 45–47 were all found to be insoluble; however, copolymerization of45 with norbornene enhanced the solubility of this polymer and its Mw and Mnwere 21,000 and 11,000, respectively (94). The polymer synthesized from ROMPof the alkyl functionalized monomer (48) had a weight-average molecular weightin excess of 300,000 (95). Cyclic voltammetry of poly(ferrocenylvinylene) formedfrom 45 showed two reversible redox waves (�E = 0.25 V), indicating interactionsbetween the iron centers. The homopolymer formed from ROMP of 45 was moreconductive than polymers of 46 and 47 (93).

The synthesis and properties of poly(ferrocenylsilanes) have been exten-sively reviewed (7,11,96). Thermal, anionic, and transition-metal-catalyzed ROPof [1]silaferrocenophanes has led to the production of polymers containing a vari-ety of functional groups attached to the silicon atoms (96–102). The structures andmorphologies of this class of polymer have been examined using X-ray diffraction,optical, atomic force, and scanning electron microscopy as well as other techniques(103–107). Pannell and co-workers have recently tested these materials as coat-ings for tapered optical-fiber gas sensors (108).

Anionic polymerization of a silicon-bridged [1]ferrocenophane using C4H9Liallowed for the preparation of living polymers which could be copolymerized witha number of different monomers (109) (eq. 14). The number-average molecularweights of polymer 50 ranged from 7700 to 21,000. Block copolymers containingdimethylsiloxane, ferrocenyldimethylsilane, and styrene groups with Mn valuesas high as 60,000 (PDI = 1.28) were also synthesized. All of the homo- and copoly-mers had two redox couples in their cyclic voltammograms, which were separatedby 0.27–0.29 V. Thermogravimetric analysis of these materials showed weightlosses beginning around 310◦C, while differential scanning calorimetry showedthat their glass-transition temperatures ranged from 103 to −127◦C (109). Fer-rocenophanes containing phosphorus (110–115), tin (116,117), germanium (118),and boron (119) bridges have also been polymerized.

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Thermal ROP of the [1]chromarenophane (52) with the [1]ferrocenophane(53) led to the formation of copolymer 54 (eq. 15); however, ROP of 52 alone did


not allow for the isolation of the corresponding chromium polymer even thoughthis monomer had significant ring strain (120).

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Multidecker transition metal complexes have been the focus of many inves-tigations in light of their electrical and magnetic properties (121–126). Opticallyactive cobalt-based systems have also been prepared by Katz and co-workers (126).Rosenblum and co-workers have described a number of different routes allowingfor the generation of face-to-face polymetallocenes (121–123). One methodology in-volved the palladium-catalyzed cross-coupling reaction of 1,8-diiodonaphthalenewith metallocenylzinc chloride (M = Fe, Ru) (122). High molecular weight, solubleface-to-face polymetallocenes were isolated by incorporating alkyl groups on thecyclopentadienyl rings (121–123). The face-to-face polyferrocene had a molecularweight in the range of 18,000 when R = H, R′ = 2-octyl, while the molecular weightof 55 when R = R′ = 2-octyl was 139,000 (121). The conductivity of polymer 55(R = H, R′ = 2-octyl) upon doping with I2 was 6.7 × 10− 3 S/cm (122). Polymersincorporating nickelocene and cobaltocene units were also synthesized; however,the solubilities of these materials were quite low. The magnetic susceptibilitiesof the Ni \Fe and Co \Fe oligomers were 3.51µB and 5.2µB, respectively, whilea nickelocene-based polymer had a magnetic moment of 5.3µB. In all cases, thevalues obtained for the polymetallocenes were greater than those of either nicke-locene or cobaltocene.

Grimes and co-workers have reported the synthesis of polymetallacarboranestaircase oligomers containing cobalt, nickel, and ruthenium (124,125). Oligomerswith up to 17 metal atoms were prepared, and electrochemical analysis of thesematerials indicated that although there was evidence for electron delocalizationwithin the tetradecker stacks, there was very little intersandwich electronic com-munication (124).


Coordination Polymers

Conjugated polymers containing metal porphyrins in their structures have poten-tial use in optical and electronic devices, solar energy conversion, and as enzymemimics (127–131). High molecular weight polymetalloporphyrins are often dif-ficult to isolate because of the poor solubility of these rigid materials. As well,the bulkiness of metalloporphyrins can inhibit the formation of an extendedπ-conjugated system. Many researchers are working on the synthesis of highmolecular weight, soluble metalloporphyrin polymers that have good film-formingproperties (127–130).

Yamamoto and co-workers have studied the synthesis of zinc porphyrin poly-mers (57) by polycondensation of 56 using Ni and Pd catalysts (128) (eq. 16).Functionalizing the zinc porphyrins and aromatic spacers with alkyl groups en-hanced the solubility of these polymers. In addition, various aromatic spacerswere studied in order to decrease the steric crowding surrounding the porphyrins.The molecular weights of these polymers were between 4600 and 37,900 (PDI =1.3–1.8), and thin films of these polymers were electrochemically active and ex-hibited electrochromism.

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Anderson and co-workers found that the microscopic polarizability of por-phyrins within polymers was 3 orders of magnitude greater than those ofmonomeric porphyrins (129). This was the largest one-photon-off-resonancethird-order optical susceptibility reported for an organic substance, and was in-dicative of inter-porphyrin conjugation. Soluble zinc polymers were synthesizedby incorporating bulky groups on the meso positions of porphyrin rings (130). Thesolubility of these polymers was very good in the presence of a small amount of acoordinating ligand such as pyridine.

The synthesis and properties of polymetallophthalocyanines have beenreviewed (132,133). Although they are structurally similar to polymetallopor-phyrins, the presence of an additional four arenes and four nitrogen atoms in theirstructures has a strong influence on the UV–vis spectra of metallophthalocyaninepolymers. These polymers can be synthesized through the metal atoms (58) (131–135), through two or more of the aromatic rings of the macrocyclic structure (59)(131–133,136), or with the phthalocyanine ring as part of a polymer side chain(60) (132,136–138). Cofacial phthalocyanine polymers are materials in which themacrocyclic rings are stacked in a “shish kebab” manner with the metals as partof the polymeric chain (58). These polymers often display excellent thermal and


chemical stability and are conducting, sometimes even in the absence of a dopingagent.

A recent report by Kimura and co-workers described the synthesis of cop-per and zinc phthalocyanine monomers substituted with either two (61) or eight(62) olefinic groups (136). Olefin metathesis of these monomers yielded a linearpolymer and a three-dimensional network, respectively.

Since the late 1950s, polymers containing metals coordinated to Schiff baseligands have been reported (139). In 1961, Goodwin and Bailar prepared Schiffbase polymers coordinated to Cu, Ni, Co, Fe, Cr, and Al ions (140). Since thattime, many more metals have been incorporated into coordination polymers pre-pared using Schiff base ligands (141–146). Archer and co-workers have studiedthe effects of different spacers on the solubility of lanthanide coordination poly-mers (142–144). The incorporation of lanthanides into polymers is important sincethese metals introduce luminescence into materials. The use of tetradentate Schiffbase ligands should shield the lanthanide ions from solvent molecules, thus de-creasing the possibility of quenching the polymers’ luminescent properties (143).These polymers (65) could be prepared via reaction of cerium ions (64) with lig-ands containing imine and phenolic groups (63) (142) (eq. 17). Analogous polymerscontaining europium and yttrium ions coordinated to bis(tetradentate) Schiff baseligands were also synthesized (143).


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Polymeric systems containing interlocking rings (catenanes) and threadedrings (rotaxanes) containing metals coordinated to their structures have beenstudied over the past few years because of their electro- and photoactivity (147–149). A polymer containing copper ions coordinated within its structure was syn-thesized via polycondensation of a dicarboxylic acid with a dialcohol derivatizedcopper(I) catenate (147). The Mw and Mn of this polymer were determined to be4,200,000 and 600,000, respectively. Swager and co-workers have reported thesynthesis of conducting polymetallorotaxanes coordinated to zinc and copper ions(148,149).

There are many examples of polymers containing transition metals coordi-nated to bipyridine and related ligands (150–164). The luminescent properties oftris(bipyridine)ruthenium(II) complexes have generated a great deal of interest inthese materials (152–158). Polymers containing metal ions coordinated to threebipyridine or substituted pyridines can contain the metal as an integral part of thepolymer skeleton (66) (165–168), pendent to the polymer backbone (67) (154–156),or in a group pendent to the polymer backbone (68) (157,158).

Rehahn and co-workers have described the synthesis of soluble ruthe-nium(II) coordination polymers by utilizing ligands that allow for the forma-tion of unbranched polymers (150,151). The molecular weights of these polymerswere in the range of 45,000, and they could be solubilized in organic or aque-ous solutions depending on their counterion. This class of polymer could be pre-pared either via complexation of pyridine ligands to ruthenium or via polycon-densation of metal-containing monomers, as shown in equation 18 (151). Petzoldand Harruna have reported the synthesis of three-dimensional high performance


coordination polymers (152,153). A number of these thermally stable, solubleruthenium-coordinated polymers were examined using optical spectroscopy.

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Polymers containing benzimidazole units in their backbones have also beenused in the synthesis of coordination metallopolymers (159–162). Osmium andruthenium coordinated polymers with bipyridine ligands have been prepared(159,160). These polymers (72, 73) possessed metal–metal interactions throughtheir conjugated backbones. Communication between the ruthenium centers of 72increased by deprotonating the imidazole protons (160). The osmium coordinatedpolymer (73) showed two reduction waves separated by 0.32 V, indicative of strongcommunication between the Os centers (159).


Metals Coordinated to the Polymer Backbone

The synthesis of polymers containing metallic moieties π -coordinated to four-,five-, and six-membered rings in their backbones has been studied. Polymers con-taining pendent cyclopentadienylcobalt moieties (76) have been prepared via di-rect reaction of monomers containing cyclopentadienylcobalt moieties coordinatedto cyclobutadiene rings (74), or via rearrangement of cobaltacyclopentadiene unitspresent in polymeric materials (75) (36–39,169–172) (eq. 19). Polymers contain-ing aromatic spacers and long chain alkyl groups pendent to the cyclobutadienerings demonstrated thermotropic liquid crystalline behavior (170,171). Bunz andco-workers have also described the synthesis of conjugated polymers containingcyclopentadienyl rings coordinated to manganese tricarbonyl units (173).

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Organometallic polymers containing arenes coordinated to metallic moietiesin their backbones have also been produced via metal complexation to organic poly-mers (174–179). Poly(9-hexylfluorene) and poly(1-hexylindene) were complexed tomanganese tricarbonyl, pentamethylcyclopentadienylcobalt, and pentamethylcy-clopentadienylrhodium moieties via η4-, η5-, and η6-coordination (174,175). Thephotoluminescence of the organometallic poly(9-hexylfluorene) had a decreasedintensity relative to its organic analogue (173).

Eyring and co-workers have reported the synthesis of organometallic poly(p-phenylene) (PPP) via reaction of the organic polymer with M(CO)3(CH3CN)3 orM(CO)6 (M = Cr, Mo) (176). It was determined that molybdenum tricarbonyl wascomplexed to about 25% of the aromatic rings of this polymer. The chromium andmolybdenum functionalized polymers demonstrated increased conductivity rela-tive to organic PPP. Nishihara and co-workers subjected poly(n-hexylphenylene)(PHP) to ligand exchange reactions to give molybdenum tricarbonyl and cyclopen-tadienyliron coordinated polymers (177–179) (eq. 20). These hexyl-substitutedpolymers displayed better solubility than metallated PPP in organic solventsas a result of the flexible alkyl chains on its backbone. Elemental analysisof the Mo(CO)3-functionalized polymer showed that 1 in every 4.8 aromaticrings was coordinated to a metallic moiety (177,178). A Cr(CO)3 coordinatedpoly(n-butylphenylene) (PBP) was also synthesized; however, this ligand exchangereaction was less efficient than when Mo(CO)3 was used (177). In the case of theorganoiron polymer, it was found that 1 in every 1.6 aromatic rings of the com-plexed PHP was coordinated to a cyclopentadienyliron moiety (179). Spectroelec-trochemical measurements of this organoiron polymer indicated the formation


of a network between aromatic rings of neighboring polymer chains followingreduction of the cationic iron centers to neutral radicals. Electrochemical andspectroscopic analysis of the organic and organometallic polymers showed thattheir conductivity increased upon metal coordination (2).

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Polymeric materials coordinated to Cr(CO)3, CpFe+, CpRu+, and Cp∗Ru+

moieties have been produced via condensation, coupling, and nucleophilic aro-matic substitution reactions. In 1987, Jin and Kim reported the synthesis ofpolyamides coordinated to chromium tricarbonyl moieties (81) via condensationreactions of phenylenediamine Cr(CO)3 (79) with various diacid chlorides (80)(180) (eq. 21). An enhancement of this polymer’s solubility was achieved via theincorporation of chromium tricarbonyl moieties pendent to its backbone. The vis-cosities of these polymers were determined in concentrated sulfuric acid and itwas found that the organometallic polymers had higher viscosities than theircorresponding organic polymers. Dembek reported that high molecular weightpolyamides coordinated to Cr(CO)3 displayed nematic liquid crystalline texture,indicating that their rigid rod nature was retained upon metal coordination eventhough their solubilities were enhanced significantly (165).

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A polyimine containing chromium tricarbonyl moieties pendent to aromaticrings in its backbone was prepared via reaction of η6-terephthaldialdehyde–Cr(CO)3 with 1,3-phenylenediamine (166). The resulting conjugated polyiminewas insoluble in common organic solvents because of the rigidity of its backbone.The synthesis of polyether/imines coordinated to cyclopentadienyliron moieties(84) has also been reported (167) (eq. 22). These polymers were prepared by re-action of a dialdehyde complex of cyclopentadienyliron (82) with a number ofaliphatic and aromatic diamines (83). These polymers were soluble in polar or-ganic solvents such as DMF and DMSO.


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Poly(phenyl ethynyls) coordinated to chromium tricarbonyl moieties (85)were synthesized via palladium-catalyzed cross-coupling of η6-1,3- and 1,4-dichloroarene chromium tricarbonyl complexes with organostannane reagents(168). Combustion analysis of these polymers indicated that their degree of poly-merization was about 18, corresponding to molecular weights of about 7800. Com-bustion and IR analysis of polymers heated past 200◦C indicated that cross-linkingreactions occurred following loss of carbon monoxide from the Cr(CO)3 moieties.Polymers with pendent metallic moieties as well as metals in their backbone (86)were also prepared (181).

The π -coordination of transition metals to haloarenes activates the aromaticring toward nucleophilic aromatic substitution reactions (182–189). In 1985, Segalreported the synthesis of soluble polyaromatic ethers coordinated to CpRu+ moi-eties (182). Dembek and co-workers later prepared a number of polyaromaticethers and thioethers coordinated to Cp∗Ru+ moieties (183,184). The synthe-sis of soluble polyaromatic ethers, thioethers, and amines via SNAr reactions ofdichloroarene complexes of cyclopentadienyliron with oxygen, sulfur, and nitro-gen based dinucleophiles has been reported (185–188) (eq. 23). Thermogravimetricanalysis of these polymers showed two distinct weight loss steps; the first one cor-responded to loss of the cyclopentadienyliron moieties while the second resultedfrom degradation of the polymer backbones (187). These polymers displayed verygood thermal stability following loss of the metallic moieties around 220◦C. Thesynthesis of polymers coordinated to CpFe+ and Cp∗Ru+ has also been reported(188).


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Polyaromatic ethers coordinated to CpFe+ moieties have also been pre-pared via sequential SNAr reactions of chloroarene complexes with hydroquinone(189). The electrochemical behavior of cationic aromatic ether, thioether, and sul-fone complexes of cyclopentadienyliron has been studied using cyclic voltam-metry and coulometry (190). Reaction of the aromatic ether complexes withsodium cyanide resulted in the formation of neutral adducts which under-went oxidative demetallation to give the corresponding organic aromatic nitriles(191).

Brammer and co-workers have reported the use of arene chromium tri-carbonyl complexes as building blocks in supramolecular assembly (192,193).Polypyrrole containing an organoiron group bonded to nitrogen has been pre-pared via chemical and electrochemical oxidation (194,195). When dicarbonyl(η5-cyclopentadienyl)(η1-pyrrolyl)iron(II) (90) was subjected to chemical oxidation, theconductivity of the resulting organometallic polypyrrole was 0.25 S/cm (194), whileoxidation with ferric chloride resulted in a polymer with a conductivity of 5.2 ×10− 5 S/cm, and electrochemical polymerization resulted in polymers with verypoor electroactivity. It was found that when the polypyrrole (91) was refluxedin either 1,2-dichloroethane or toluene, an azoferrocene-based polymer (92) wasformed (195) (eq. 24).

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It has been reported that polymers with silole units in their backbones be-came coordinated to iron tricarbonyl when they were irradiated with UV light in


the presence of Fe(CO)5 (196). This polymer was redshifted relative to its organicanalogue, and was conducting upon doping.

Metallic Moieties in the Polymer Side Chains

As early as 1955, the synthesis of poly(ferrocenylethylene) was reported (197), andinterest in this class of polymer is still increasing (1,3–6). Pittman and co-workersdescribed the synthesis and polymerization of a number of ferrocene-basedmonomers containing acrylate and methacrylate functionalities (93) (198). Thepolymerization of vinylferrocene and 3-vinylbisfulvalenediiron was also per-formed in order to study the electrical properties of these polymers (199).Upon oxidation of the polymer formed from the radical polymerization of3-vinylbisfulvalenediiron, the conductivity of this mixed valence polymer was be-tween 6 × 10− 3 and 9 × 10− 3 �− 1·cm− 1. Monomers of chromium and iron tricar-bonyl (94, 95) were also homo- and copolymerization to give their correspondingorganometallic polymers (200,201).

Functionalization of organometallic monomers containing olefinic groupshas led to the production of organometallic polymers possessing interestingproperties. Polymerization of organoiron monomers resulted in the productionof liquid crystalline polymers containing ferrocene units in their side chains(96) (202–204). The nonlinear optical properties of polymers containing ferro-cenyl groups in pendent groups have also been examined (205). The electro-chemical behavior of ferrocenyl functionalized polymers has also been of interest(206). Neuse and co-workers have found that water-soluble ferrocene function-alized polymers possess interesting antiproliferative properties (97) (207–209).Coordination of Ru+Cp∗, Ru+C8H11, or Ru+H(PCy3)2 to the aromatic rings ofpolystyrene has been reported (210). Depending on the bulkiness of the ligandattached to ruthenium, anywhere from 25 to 100% of the aromatic rings in thepolymers became complexed to the ruthenium moieties. Recently, polymethacry-lates with cationic cyclopentadienyliron moieties coordinated to their side chains(98) were prepared via radical polymerization of their corresponding organoironmonomers (211). Photolytic demetallation of the cyclopentadienyliron-coordinatedpolymethacrylates resulted in the isolation of the corresponding organic ana-logues, whose Mw’s ranged from 48,000 to 68,000. Other examples of metalσ -bonded (99, 100) and coordinated (101) monomers have also been examined(212–214).


Allcock and co-workers have described the ROP of cyclic phosphazenescontaining ferrocenyl units, resulting in the isolation of the correspondingorganometallic polymers (102) (215). Polyphosphazenes containing chromiumtricarbonyl units in their side chains were also isolated following ROP ofan inorganic monomer, and subsequent functionalization of this polymer withchromium tricarbonyl (103) (216). Differential scanning calorimetry showed thatthe glass-transition temperatures of the Cr(CO)3 functionalized polymers werehigher than their organic analogues by approximately 50◦C.


The ROP of ansa- and spirocyclic ansa-zirconocene complexes has beenreported (217) (eq. 25). Polycarbosilane [(CH2)3Si(η5-C5H4)2ZrCl2]n (105) wasobtained from reaction of the spirocyclic silacyclobutane-bridged monomer(CH2)3Si(η5-C5H4)2ZrCl2 (104) with Karstedt’s catalyst. This polymer demon-strated moderate activity as a catalyst for ethylene polymerization.

(25)

The ROMP of norbornenes functionalized with neutral ferrocenyl moi-eties has been reported; the aim was to prepare redox-active polymers (218,219) (eq. 26). The synthesis of polynorbornenes functionalized with cationiccyclopentadienyliron-coordinated aryl ethers has also been reported (220). Demet-allation of metallated norbornenes and polynorbornenes led to the liberation oftheir organic analogues (221–223). Electrochemical analysis of the metallatedpolymers showed that the cationic iron centers were reduced between −1.2 and−1.4 V.

(26)


Dendrimers and Star Polymers

There has been considerable interest directed toward the synthesis oforganometallic star polymers and dendrimers in recent years (see DENDRONIZED

POLYMERS). The production of highly ordered, highly branched organometallic ma-terials is of importance due to their electronic, optical, and biomedical applications(224–232).

Dendritic poly(aryl ethers) containing up to 24 peripheral ferrocenyl unitshave been synthesized using a stepwise convergent methodology (233). Cyclicvoltammetry of these dendrimers showed that the iron centers were all reversiblyoxidized around E 1

2= 0.21 V. Astruc and co-workers have explored the synthesis

and properties of a number of different classes of ferrocene-based star polymersand dendrimers (234–238). A dendrimer containing 54 ferrocene units at its pe-riphery was synthesized and reversible oxidation of all 54 iron centers was ob-served (234). Chemical oxidation of the neutral iron centers to cationic speciescould also be accomplished using NOPF6. Dendrimers containing 243 ferrocenylunits at the periphery were also synthesized via ferrocenylsilation reactions of al-lyl terminated dendrimers (235). Nonametallic dendrimers containing ferrocenyl(237) or cobaltocenium (238) moieties (108) at their periphery were synthesized viareaction of amine functionalized dendrimers with the acid chlorides of ferroceneor cobaltocene. Deschenaux and co-workers have been investigating the synthesisof ferrocenyl-based polymers with liquid crystalline properties (239,240).


Cuadrado and co-workers have also been active in the synthesis of den-drimers containing ferrocene and cobaltocene moieties (241–244). The synthesisof propylenimine-based dendrimers with up to five generations and 64 periph-eral ferrocenyl moieties underwent reversible oxidation processes at E 1

2= 0.59 V

(241,242). The guest–host relationship of some low generation dendrimers with cy-clodextrins was examined (241). Silicon-based ferrocenyl dendrimers possessingelectrochemical communication between the iron centers were also synthesized(243).

Moss and co-workers have been synthesizing dendrimers containing Ru Cσ -bonds using a convergent approach (245). A fourth-generation dendrimer con-taining 48 organometallic moieties was prepared using complexes such as 109 asstarting materials.

There has been a great deal of interest in the design of dendrimers usingarene complexes of transition metals (246–252). Astruc has developed an efficientroute to core molecules suitable for the synthesis of star and dendritic materialsvia peralkylation or allylation of methyl-substituted arene complexes of cyclopen-tadienyliron. The resulting branched polymers contained cationic cyclopentadi-enyliron moieties at the core and/or the periphery. Complexes containing arylethers coordinated to six CpFe+ moieties (110) were synthesized via SNAr reac-tions (248).


The synthesis of a water-soluble metallodendrimer containing six cationiccyclopentadienyliron moieties was also reported (249). This dendrimer was ex-amined as a redox catalyst for the cathodic reduction of nitrates and nitritesto ammonia. Star-shaped polyaromatic ether complexes of cyclopentadienylironwere recently reported by Abd-El-Aziz and co-workers (250). These complexes con-tained up to 15 cationic cyclopentadienyliron moieties pendent to aromatic ringsin the star branches (111). Electrochemical analysis of these star polymers showedthat the iron centers underwent reversible reduction processes.


The synthesis of organosilane dendrimers coordinated to up to 72 Cp∗Ru+

moieties has been reported by Tilley and co-workers (251). Mass spectrometryof the dendrimer coordinated to 72 positively charged ruthenium moieties (112)revealed that although the desired complex was present in the sample, completecoordination of the aromatic rings may have been hindered because of steric crowd-ing. Organosilicon dendrimers containing chromium tricarbonyl moieties pendentto peripheral aromatic rings have also been synthesized (252). Cyclic voltamme-try of these materials showed that oxidation of the chromium atoms occurred re-versibly in the absence of nucleophilic species, and that the chromium tricarbonylunits behaved as isolated redox centers.

There are numerous examples of dendrimers and star polymers containingmetal coordination complexes (253–259). The synthesis of polypyridine rutheniumcoordination complexes incorporating Fe and Co (113) has been established (255).A ruthenium star-shaped complex with a CpFe+-coordinated arene as the corehas also been reported (254).


Platinum (260–262) and palladium (262,263) complexes have been incor-porated into dendrimeric materials. Polymers incorporating both platinum andpalladium units coordinated to bipyridine ligands have been reported by Pudde-phatt and co-workers (114) (262). These dendrimers were prepared via oxidativeaddition of a C Br bond to a platinum complex, giving the core molecule. Fur-ther reaction with platinum or palladium complexes resulted in the homo- orheterometallic materials, respectively.


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ALAA S. ABD-EL-AZIZ

The University of Winnipeg

METALLOCENE CATALYSTS. See SINGLE-SITE CATALYSTS

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