METAL-CONTAINING POLYMERS

Introduction

The development of organometallic chemistry in the 1950s has played an
important role in the redefinition of polymer chemistry. While organic and
inorganic polymers (qv) were previously the only two classes of macromolecules,
the introduction of metals into polymers marked the beginning of a new field of
research (see I

NORGANIC

P

OLYMERS

). The combination of polymeric and metallic

properties has caused a surging interest in the development of metal-containing
polymers over the past few decades (1–5). It is well known that depending on
the elements and the types of bonding present, the properties of these polymers
differ dramatically. The degree of polymerization and the nature of the metal also
have strong influences on the properties of polymeric materials. It is the diverse
array of electrical, electrochemical, magnetic, optical, and catalytic properties
that define the applications of metal-containing polymers.

In recent years, many reviews have been dedicated to advances in the field of

metal-containing polymers (6–14). Although this article classifies these polymers
according to their structures, many of these polymers could have been included
in more than one section. The aim of this work is to give an overview of the
synthesis, properties, and applications of metal-containing polymers, with a focus
on 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 been

studied in recent years because of their electrical and optical properties (14,15).
This class of organometallic polymers can be prepared via reactions occurring

1

Encyclopedia 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, and
analysis of 3 indicates that their degree of polymerization is between 8 and 13 (16).

(1)

Many different transition metals have been incorporated into polymers con-

taining C C triple bonds in order to enhance metal d

π–pπ

∗

back bonding, which

is expected to contribute to

π-electron delocalization (17–30). Although much of

the 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) has
been 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 many
organic materials (

<1 eV) (20). Lewis and co-workers demonstrated that incorpo-

rating alternating electron donor and acceptor groups into platinum acetylide
polymers resulted in materials with band gaps below 2 eV (20). Equation 3
shows 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 average
molecular weight of 173,000 (25).

(2)

Reaction of terminal al kynes (7) with transition metal halides (8) in the

presence 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 controlled
through the choice of phosphine ligands at the gold centers.

(3)

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 the
reaction (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.

(4)

In 1973, the synthesis of titanium, zirconium, and hafnium polyesters via reaction
of the dicyclopentadienylmetal dichloride complexes with disodium dicarboxylates
in either aqueous or organic solvents was reported (31). Around the same time the
synthesis of polyethers and amines of titanocene and polythioethers of zirconocene
was 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 while
maintaining the integrity of the polymers. The synthesis of polymers containing
cobaltacyclopentadiene groups within their backbones has also been investigated
(36–39).

(5)

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

4

METAL-CONTAINING POLYMERS

Vol. 7

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

(6)

Cuadrado and co-workers have prepared a polymer with Fe Fe bonds in

its structure (19) via reaction of a polysiloxane with Fe(CO)

5

(44). The insoluble

nature of this polymer indicated that cross-linking between polysiloxane chains
occurred upon formation of the organoiron polymer. Silicon polymers containing
Co Co bonds (20) have been prepared via the reaction of Co

2

(CO)

8

with the triple

bonds of a silicon based polymer (45). Mixed metal systems were also described
in which complexes containing arenes coordinated to chromium tricarbonyl were
reacted with Mo

2

Cp

2

(CO)

6

or Co

2

(CO)

8

.

Polymeric materials containing Pt Pt bonds in their backbones have been

examined (46). The formation of platinum polymers (23) was achieved via reaction
of the platinum complex (21) with diacetylides, diphosphines, or diisocyanides (22)
(eq. 7).

(7)

Vol. 7

METAL-CONTAINING POLYMERS

5

Polymers whose backbones consisted solely of metal–metal bonds have been

synthesized by electrochemical reduction of ruthenium and osmium complexes
(47,48). Reduction of [M

II

(trans-Cl

2

)(bipy)(CO)

2

] (M

= Ru, Os) (24) to M

0

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 were
selective for the reduction of carbon dioxide.

(8)

Polymers containing metal–metal single (26) and multiple bonds (27) have

also been prepared via reaction of bimetallic carboxylates with coordinating lig-
ands (49–53). It has been found that polymeric materials containing Mo Mo triple
bonds crystallize from solutions of Mo

2

(O

2

CCH

3

)

4

in bidentate ligands such as

1,2-bis(dimethylphosphino)ethane or tetramethylenediamine (53).

π-Coordinated Systems, Metallocene-Based Systems

Polymerization of ferrocene derivatives marked the beginning of a new era
in polymer chemistry (54). In the early 1960s, Korshak and Nesmeyanov re-
ported the synthesis of ferrocene-based polymers by reacting ferrocene with
tert-butyl hydroperoxide (55,56). Neuse later reported that these polymers con-
sisted of homoannular and heteroannular aliphatic ether-substituted units with
number-average molecular weights less than 7000 (57). Methodologies using
metal 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). The

conductivity of this crystalline polymer was higher than the conductivity of amor-
phous polyferrocenylene. In 1996, Nishihara and co-workers synthesized a soluble
1,1



-dihexylferrocene-based polymer and its electrochemical properties and pho-

toconductivity were examined (63).

6

METAL-CONTAINING POLYMERS

Vol. 7

The synthesis and polymerization of a mercuriferrocene complex was re-

ported in 1963 (64). Decomposition of this polymer gave 1,1



-diiodoferrocene or

1,1



-ferrocenedicarboxylic acid along with other products. It was later reported

that poly(mercuriferrocenylene) could be converted to polyferrocenylene by react-
ing the poly(mercuriferrocenylene) with ferrocene at 245–260

◦

C (65). Polymers

prepared via reaction of ferrocenes functionalized with carboxylic acids, acid chlo-
rides, alcohols, and amines have been utilized to synthesize condensation polymers
containing ferrocenyl units in their backbones (54,66–69). In 1984, Rausch and
co-workers reported the synthesis of polyamides and polyureas from the reaction
of 1,1



-bis(

β-aminoethyl)ferrocene (28) with diisocyanates (29) or diacid chlorides

(30) (66) (eq. 9).

(9)

More recently, a soluble polymer (32) was prepared via reaction of

1,1



-ferrocenedimethanol with 4,4



-biphenyltetraamine in the presence of

[RuCl

2

(P(C

6

H

5

)

3

)

3

] (70). Approximately 20% of the iron centers were found to

be in the Fe(III) state as a result of oxidation by ruthenium complexes formed
during the polycondensation reaction. Wright and co-workers have reported the
synthesis of ferrocene-based polymers possessing nonlinear optical properties (33)
(71–73). These polymers were formed by polycondensation of a difunctionalized
ferrocene 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 cobalt
units 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

Vol. 7

METAL-CONTAINING POLYMERS

7

acid complex of cobaltocenium with the corresponding organometallic monomers
(32,75). Cuadrado and co-workers prepared polyamides containing siloxane
bridges (36) via condensation of 1,1



-bis(chlorocarbonyl)cobaltocenium hexaflu-

orophosphate (34) with a siloxane-based diamine (35) (76) (eq. 10). This polymer
displayed very limited solubility in polar organic solvents; however, the analogous
ferrocene-based polymer had an M

n

value of 10,600 (77). These ferrocene-based

polymers were utilized in the production of chemically modified electrodes.

(10)

The synthesis of conjugated polymers containing ferrocene units in their

backbones has received much attention in recent years (78–81). Bochmann
and co-workers have described the synthesis of ferrocene-based polymers via
palladium-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 dilithio

bis(3-hexyl-4-methylcyclopentadienide)arylenes (38) with ferrous iodide (82). Us-
ing a similar strategy, poly(ferrocenylsilane) was prepared by reaction of the
dilithium salt of dicyclopentadienyldimethylsilane (38, R

= Si(CH

3

)

2

, R



, R



=

H) with ferrous chloride (83) (eq. 11).

(11)

8

METAL-CONTAINING POLYMERS

Vol. 7

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 by
ring-opening polymerization (ROP) and desulfurization of [3]-trithiaferrocenenes
(41) (85–87) (eq. 12). High molecular weight linear and network poly(ferrocene
persulfides) were produced by reaction of the trithiaferrocenenes with P(C

4

H

9

)

3

.

(12)

The ROP of [1]thia- and [1]selenaferrocenophanes has been accomplished

thermally and in the presence of anionic initiators; however, the resulting
polymers were insoluble (88). Methylation of the cyclopentadienyl rings of
the [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 found
that these polymers possessed stronger Fe Fe interactions than the analogous
silicon-bridged materials (88). Polyferrocenes containing sulfide linkages were
also prepared via thermal and cationic ROP of [2]carbathioferrocenophane (89).

Metallocenophanes containing hydrocarbon bridges have been polymerized

thermally 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 was
hydrogen, the resulting polymers were insoluble, whereas isomeric mixtures of
43 (R

= CH

3

) resulted in soluble polymetallocenes (44). Cyclic voltammetry of

the poly(ruthenocenylethylenes) showed irreversible oxidation processes at 0.60
V, while poly(ferrocenylethylenes) underwent reversible oxidation processes at
−0.27 V (92).

(13)

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

Vol. 7

METAL-CONTAINING POLYMERS

9

from ROMP of 45–47 were all found to be insoluble; however, copolymerization of
45 with norbornene enhanced the solubility of this polymer and its M

w

and M

n

were 21,000 and 11,000, respectively (94). The polymer synthesized from ROMP
of the alkyl functionalized monomer (48) had a weight-average molecular weight
in excess of 300,000 (95). Cyclic voltammetry of poly(ferrocenylvinylene) formed
from 45 showed two reversible redox waves (

E = 0.25 V), indicating interactions

between the iron centers. The homopolymer formed from ROMP of 45 was more
conductive 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 ROP
of [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 and
morphologies 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 C

4

H

9

Li

allowed for the preparation of living polymers which could be copolymerized with
a number of different monomers (109) (eq. 14). The number-average molecular
weights of polymer 50 ranged from 7700 to 21,000. Block copolymers containing
dimethylsiloxane, ferrocenyldimethylsilane, and styrene groups with M

n

values

as 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 separated
by 0.27–0.29 V. Thermogravimetric analysis of these materials showed weight
losses beginning around 310

◦

C, while differential scanning calorimetry showed

that 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.

(14)

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

10

METAL-CONTAINING POLYMERS

Vol. 7

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

(15)

Multidecker transition metal complexes have been the focus of many inves-

tigations in light of their electrical and magnetic properties (121–126). Optically
active cobalt-based systems have also been prepared by Katz and co-workers (126).
Rosenblum and co-workers have described a number of different routes allowing
for the generation of face-to-face polymetallocenes (121–123). One methodology in-
volved the palladium-catalyzed cross-coupling reaction of 1,8-diiodonaphthalene
with metallocenylzinc chloride (M

= Fe, Ru) (122). High molecular weight, soluble

face-to-face polymetallocenes were isolated by incorporating alkyl groups on the
cyclopentadienyl rings (121–123). The face-to-face polyferrocene had a molecular
weight in the range of 18,000 when R

= H, R



= 2-octyl, while the molecular weight

of 55 when R

= R



= 2-octyl was 139,000 (121). The conductivity of polymer 55

(R

= H, R



= 2-octyl) upon doping with I

2

was 6.7

× 10

− 3

S/cm (122). Polymers

incorporating nickelocene and cobaltocene units were also synthesized; however,
the solubilities of these materials were quite low. The magnetic susceptibilities
of the Ni

\Fe and Co \Fe oligomers were 3.51µ

B

and 5.2

µ

B

, respectively, while

a nickelocene-based polymer had a magnetic moment of 5.3

µ

B

. In all cases, the

values obtained for the polymetallocenes were greater than those of either nicke-
locene or cobaltocene.

Grimes and co-workers have reported the synthesis of polymetallacarborane

staircase oligomers containing cobalt, nickel, and ruthenium (124,125). Oligomers
with up to 17 metal atoms were prepared, and electrochemical analysis of these
materials indicated that although there was evidence for electron delocalization
within the tetradecker stacks, there was very little intersandwich electronic com-
munication (124).

Vol. 7

METAL-CONTAINING POLYMERS

11

Coordination Polymers

Conjugated polymers containing metal porphyrins in their structures have poten-
tial use in optical and electronic devices, solar energy conversion, and as enzyme
mimics (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 extended
π-conjugated system. Many researchers are working on the synthesis of high
molecular weight, soluble metalloporphyrin polymers that have good film-forming
properties (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 spacers
were 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.

(16)

Anderson and co-workers found that the microscopic polarizability of por-

phyrins within polymers was 3 orders of magnitude greater than those of
monomeric porphyrins (129). This was the largest one-photon-off-resonance
third-order optical susceptibility reported for an organic substance, and was in-
dicative of inter-porphyrin conjugation. Soluble zinc polymers were synthesized
by incorporating bulky groups on the meso positions of porphyrin rings (130). The
solubility of these polymers was very good in the presence of a small amount of a
coordinating ligand such as pyridine.

The synthesis and properties of polymetallophthalocyanines have been

reviewed (132,133). Although they are structurally similar to polymetallopor-
phyrins, the presence of an additional four arenes and four nitrogen atoms in their
structures has a strong influence on the UV–vis spectra of metallophthalocyanine
polymers. 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 the
macrocyclic rings are stacked in a “shish kebab” manner with the metals as part
of the polymeric chain (58). These polymers often display excellent thermal and

12

METAL-CONTAINING POLYMERS

Vol. 7

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

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 linear
polymer and a three-dimensional network, respectively.

Since the late 1950s, polymers containing metals coordinated to Schiff base

ligands have been reported (139). In 1961, Goodwin and Bailar prepared Schiff
base polymers coordinated to Cu, Ni, Co, Fe, Cr, and Al ions (140). Since that
time, many more metals have been incorporated into coordination polymers pre-
pared using Schiff base ligands (141–146). Archer and co-workers have studied
the effects of different spacers on the solubility of lanthanide coordination poly-
mers (142–144). The incorporation of lanthanides into polymers is important since
these metals introduce luminescence into materials. The use of tetradentate Schiff
base 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 polymers
containing europium and yttrium ions coordinated to bis(tetradentate) Schiff base
ligands were also synthesized (143).

Vol. 7

METAL-CONTAINING POLYMERS

13

(17)

Polymeric systems containing interlocking rings (catenanes) and threaded

rings (rotaxanes) containing metals coordinated to their structures have been
studied 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 derivatized
copper(I) catenate (147). The M

w

and M

n

of this polymer were determined to be

4,200,000 and 600,000, respectively. Swager and co-workers have reported the
synthesis 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 of
tris(bipyridine)ruthenium(II) complexes have generated a great deal of interest in
these materials (152–158). Polymers containing metal ions coordinated to three
bipyridine or substituted pyridines can contain the metal as an integral part of the
polymer 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 polymers
were 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). Petzold
and Harruna have reported the synthesis of three-dimensional high performance

14

METAL-CONTAINING POLYMERS

Vol. 7

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

(18)

Polymers containing benzimidazole units in their backbones have also been

used in the synthesis of coordination metallopolymers (159–162). Osmium and
ruthenium coordinated polymers with bipyridine ligands have been prepared
(159,160). These polymers (72, 73) possessed metal–metal interactions through
their conjugated backbones. Communication between the ruthenium centers of 72
increased by deprotonating the imidazole protons (160). The osmium coordinated
polymer (73) showed two reduction waves separated by 0.32 V, indicative of strong
communication between the Os centers (159).

Vol. 7

METAL-CONTAINING POLYMERS

15

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 coordinated
to cyclobutadiene rings (74), or via rearrangement of cobaltacyclopentadiene units
present in polymeric materials (75) (36–39,169–172) (eq. 19). Polymers contain-
ing aromatic spacers and long chain alkyl groups pendent to the cyclobutadiene
rings demonstrated thermotropic liquid crystalline behavior (170,171). Bunz and
co-workers have also described the synthesis of conjugated polymers containing
cyclopentadienyl rings coordinated to manganese tricarbonyl units (173).

(19)

Organometallic polymers containing arenes coordinated to metallic moieties

in their backbones have also been produced via metal complexation to organic poly-
mers (174–179). Poly(9-hexylfluorene) and poly(1-hexylindene) were complexed to
manganese tricarbonyl, pentamethylcyclopentadienylcobalt, and pentamethylcy-
clopentadienylrhodium moieties via

η

4

-,

η

5

-, and

η

6

-coordination (174,175). The

photoluminescence of the organometallic poly(9-hexylfluorene) had a decreased
intensity 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

(CH

3

CN)

3

or

M(CO)

6

(M

= Cr, Mo) (176). It was determined that molybdenum tricarbonyl was

complexed to about 25% of the aromatic rings of this polymer. The chromium and
molybdenum 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-substituted
polymers displayed better solubility than metallated PPP in organic solvents
as a result of the flexible alkyl chains on its backbone. Elemental analysis
of the Mo(CO)

3

-functionalized polymer showed that 1 in every 4.8 aromatic

rings was coordinated to a metallic moiety (177,178). A Cr(CO)

3

coordinated

poly(n-butylphenylene) (PBP) was also synthesized; however, this ligand exchange
reaction was less efficient than when Mo(CO)

3

was used (177). In the case of the

organoiron 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

16

METAL-CONTAINING POLYMERS

Vol. 7

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

(20)

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 of
polyamides coordinated to chromium tricarbonyl moieties (81) via condensation
reactions of phenylenediamine Cr(CO)

3

(79) with various diacid chlorides (80)

(180) (eq. 21). An enhancement of this polymer’s solubility was achieved via the
incorporation of chromium tricarbonyl moieties pendent to its backbone. The vis-
cosities of these polymers were determined in concentrated sulfuric acid and it
was found that the organometallic polymers had higher viscosities than their
corresponding organic polymers. Dembek reported that high molecular weight
polyamides coordinated to Cr(CO)

3

displayed nematic liquid crystalline texture,

indicating that their rigid rod nature was retained upon metal coordination even
though their solubilities were enhanced significantly (165).

(21)

A polyimine containing chromium tricarbonyl moieties pendent to aromatic

rings in its backbone was prepared via reaction of

η

6

-terephthaldialdehyde–

Cr(CO)

3

with 1,3-phenylenediamine (166). The resulting conjugated polyimine

was 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 of
aliphatic and aromatic diamines (83). These polymers were soluble in polar or-
ganic solvents such as DMF and DMSO.

Vol. 7

METAL-CONTAINING POLYMERS

17

(22)

Poly(phenyl ethynyls) coordinated to chromium tricarbonyl moieties (85)

were synthesized via palladium-catalyzed cross-coupling of

η

6

-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-linking

reactions 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 aromatic

ring toward nucleophilic aromatic substitution reactions (182–189). In 1985, Segal
reported the synthesis of soluble polyaromatic ethers coordinated to CpRu

+

moi-

eties (182). Dembek and co-workers later prepared a number of polyaromatic
ethers and thioethers coordinated to Cp

∗

Ru

+

moieties (183,184). The synthe-

sis of soluble polyaromatic ethers, thioethers, and amines via S

N

Ar reactions of

dichloroarene complexes of cyclopentadienyliron with oxygen, sulfur, and nitro-
gen based dinucleophiles has been reported (185–188) (eq. 23). Thermogravimetric
analysis of these polymers showed two distinct weight loss steps; the first one cor-
responded to loss of the cyclopentadienyliron moieties while the second resulted
from degradation of the polymer backbones (187). These polymers displayed very
good thermal stability following loss of the metallic moieties around 220

◦

C. The

synthesis of polymers coordinated to CpFe

+

and Cp

∗

Ru

+

has also been reported

(188).

18

METAL-CONTAINING POLYMERS

Vol. 7

(23)

Polyaromatic ethers coordinated to CpFe

+

moieties have also been pre-

pared via sequential S

N

Ar 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 with
sodium 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(

η

5

-

cyclopentadienyl)(

η

1

-pyrrolyl)iron(II) (90) was subjected to chemical oxidation, the

conductivity of the resulting organometallic polypyrrole was 0.25 S/cm (194), while
oxidation with ferric chloride resulted in a polymer with a conductivity of 5.2

×

10

− 5

S/cm, and electrochemical polymerization resulted in polymers with very

poor electroactivity. It was found that when the polypyrrole (91) was refluxed
in either 1,2-dichloroethane or toluene, an azoferrocene-based polymer (92) was
formed (195) (eq. 24).

(24)

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

Vol. 7

METAL-CONTAINING POLYMERS

19

the presence of Fe(CO)

5

(196). This polymer was redshifted relative to its organic

analogue, and was conducting upon doping.

Metallic Moieties in the Polymer Side Chains

As early as 1955, the synthesis of poly(ferrocenylethylene) was reported (197), and
interest in this class of polymer is still increasing (1,3–6). Pittman and co-workers
described the synthesis and polymerization of a number of ferrocene-based
monomers containing acrylate and methacrylate functionalities (93) (198). The
polymerization 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 of
3-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 corresponding
organometallic polymers (200,201).

Functionalization of organometallic monomers containing olefinic groups

has led to the production of organometallic polymers possessing interesting
properties. Polymerization of organoiron monomers resulted in the production
of 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

+

C

8

H

11

, or Ru

+

H(PCy

3

)

2

to the aromatic rings of

polystyrene has been reported (210). Depending on the bulkiness of the ligand
attached to ruthenium, anywhere from 25 to 100% of the aromatic rings in the
polymers 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 organoiron
monomers (211). Photolytic demetallation of the cyclopentadienyliron-coordinated
polymethacrylates resulted in the isolation of the corresponding organic ana-
logues, whose M

w

’s ranged from 48,000 to 68,000. Other examples of metal

σ-bonded (99, 100) and coordinated (101) monomers have also been examined
(212–214).

20

METAL-CONTAINING POLYMERS

Vol. 7

Allcock and co-workers have described the ROP of cyclic phosphazenes

containing ferrocenyl units, resulting in the isolation of the corresponding
organometallic polymers (102) (215). Polyphosphazenes containing chromium
tricarbonyl units in their side chains were also isolated following ROP of
an inorganic monomer, and subsequent functionalization of this polymer with
chromium tricarbonyl (103) (216). Differential scanning calorimetry showed that
the glass-transition temperatures of the Cr(CO)

3

functionalized polymers were

higher than their organic analogues by approximately 50

◦

C.

Vol. 7

METAL-CONTAINING POLYMERS

21

The ROP of ansa- and spirocyclic ansa-zirconocene complexes has been

reported (217) (eq. 25). Polycarbosilane [(CH

2

)

3

Si(

η

5

-C

5

H

4

)

2

ZrCl

2

]

n

(105) was

obtained from reaction of the spirocyclic silacyclobutane-bridged monomer
(CH

2

)

3

Si(

η

5

-C

5

H

4

)

2

ZrCl

2

(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 cationic
cyclopentadienyliron-coordinated aryl ethers has also been reported (220). Demet-
allation of metallated norbornenes and polynorbornenes led to the liberation of
their organic analogues (221–223). Electrochemical analysis of the metallated
polymers showed that the cationic iron centers were reduced between

−1.2 and

−1.4 V.

(26)

22

METAL-CONTAINING POLYMERS

Vol. 7

Dendrimers and Star Polymers

There has been considerable interest directed toward the synthesis of
organometallic star polymers and dendrimers in recent years (see D

ENDRONIZED

P

OLYMERS

). 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 units

have been synthesized using a stepwise convergent methodology (233). Cyclic
voltammetry of these dendrimers showed that the iron centers were all reversibly
oxidized 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 polymers
and 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 species
could also be accomplished using NOPF

6

. Dendrimers containing 243 ferrocenyl

units 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 via
reaction of amine functionalized dendrimers with the acid chlorides of ferrocene
or cobaltocene. Deschenaux and co-workers have been investigating the synthesis
of ferrocenyl-based polymers with liquid crystalline properties (239,240).

Vol. 7

METAL-CONTAINING POLYMERS

23

Cuadrado and co-workers have also been active in the synthesis of den-

drimers containing ferrocene and cobaltocene moieties (241–244). The synthesis
of 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 possessing
electrochemical communication between the iron centers were also synthesized
(243).

Moss and co-workers have been synthesizing dendrimers containing Ru C

σ-bonds using a convergent approach (245). A fourth-generation dendrimer con-
taining 48 organometallic moieties was prepared using complexes such as 109 as
starting materials.

There has been a great deal of interest in the design of dendrimers using

arene complexes of transition metals (246–252). Astruc has developed an efficient
route to core molecules suitable for the synthesis of star and dendritic materials
via 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 aryl
ethers coordinated to six CpFe

+

moieties (110) were synthesized via S

N

Ar reac-

tions (248).

24

METAL-CONTAINING POLYMERS

Vol. 7

The synthesis of a water-soluble metallodendrimer containing six cationic

cyclopentadienyliron moieties was also reported (249). This dendrimer was ex-
amined as a redox catalyst for the cathodic reduction of nitrates and nitrites
to ammonia. Star-shaped polyaromatic ether complexes of cyclopentadienyliron
were recently reported by Abd-El-Aziz and co-workers (250). These complexes con-
tained up to 15 cationic cyclopentadienyliron moieties pendent to aromatic rings
in the star branches (111). Electrochemical analysis of these star polymers showed
that the iron centers underwent reversible reduction processes.

Vol. 7

METAL-CONTAINING POLYMERS

25

The synthesis of organosilane dendrimers coordinated to up to 72 Cp

∗

Ru

+

moieties has been reported by Tilley and co-workers (251). Mass spectrometry
of the dendrimer coordinated to 72 positively charged ruthenium moieties (112)
revealed that although the desired complex was present in the sample, complete
coordination of the aromatic rings may have been hindered because of steric crowd-
ing. Organosilicon dendrimers containing chromium tricarbonyl moieties pendent
to 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 tricarbonyl
units behaved as isolated redox centers.

There are numerous examples of dendrimers and star polymers containing

metal coordination complexes (253–259). The synthesis of polypyridine ruthenium
coordination complexes incorporating Fe and Co (113) has been established (255).
A ruthenium star-shaped complex with a CpFe

+

-coordinated arene as the core

has also been reported (254).

26

METAL-CONTAINING POLYMERS

Vol. 7

Platinum (260–262) and palladium (262,263) complexes have been incor-

porated into dendrimeric materials. Polymers incorporating both platinum and
palladium units coordinated to bipyridine ligands have been reported by Pudde-
phatt and co-workers (114) (262). These dendrimers were prepared via oxidative
addition 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- or
heterometallic materials, respectively.

Vol. 7

METAL-CONTAINING POLYMERS

27

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