Catalytic Polymerization of Phenylacetylene by Cationic

Rhodium and Iridium Complexes of Ferrocene-Based

Ligands

SANG-ILL LEE, SANG-CHUL SHIM, and TAE-JEONG K I M *

Department of Industrial Chemistry, Kyungpook National University, Taegu, Korea 702-701

SYNOPSIS

Some new Rh(1) and Ir(1) complexes of the types [(COD)M(LL)]ClO, and [(COD)MCI],
[COD = cyclooctadiene; M = Rh, Ir; LL = 1,l'-bis(dipheny1phosphino)ferrocene (DPPF),
1-diphenylphosphino-2-(N,N-dimethylamino)methylferrocene (FcNP), 1,6-diferrocenyl-2,5-
diazahexane (FcNN)] were prepared, and their catalytic activities toward polymerization
of phenyl acetylene were examined. The rhodium complexes proved to be very effective
catalysts to yield highly stereoregular polyphenylacetylene (cis-transoidal-PPA) in high
yields under mild conditions. The number-average molecular weight (A?,) of the PPA ob-
tained is in the range of 19,000-33,000 and the weight-average molecular weight (A?=)is
in the range of 47,000-95,000. Comparative studies revealed that of various catalysts em-
ployed, the cationic mononuclear [Rh(FcNN)(COD)]CIO,complex exhibited the best results
to give exclusively the cis-transoidal-PPA (cis content -
100%)with the highest molecular
weight (A?,= 33,340) in the highest chemical yield (94%). Other reaction parameters such
as the softness of the ligand, the solvent, the relative amount of catalyst, and the reaction
temperature were also investigated to find that all these factors played crucial roles. The
iridium systems worked better for the trimerization rather than polymerization to yield

-
1,3,5-triphenybenzene as major product. 0 1996 John Wiley & Sons, Inc.
Keywords: polyphenylacetylene rhodium catalyst iridium catalyst ferrocenylimine
ferrocenylphosphine

INTRODUCTION
For the past decade there has been a great deal of
interest in the synthesis of polyacetylene derivatives
due to their conducting properties.'-4 Polymerization
of phenylacetylene has been attempted under var-
ious conditions, e.g., by radical (thermal initiation,
high-energy radiation, and peroxide):-' cationic
(protonic acids, and metal halides),"-14 and coor-
dination mechanism^.'^-^^ However, the polymer-
izations have often been accompanied by some of
the following problems: (i) the molecular weight of
the polyphenylacetylene was low (usually less than
3000), (ii) the product involved a methanol-soluble
oligomer and/or a benzene-insoluble fraction, (iii)
a dimer and cyclic trimer were formed as by-prod-
* To whom all correspondence should be addressed.
.Journal of Polymer Science: Part A Polymer Chemistry, Vol. 34,2377-2386 (1996)
0 1996 John Wiley & Sons, Inc. CCC OS87-624X/96/122377-10
ucts; and (iv) the reaction required a long time and/
or high temperature.
Yet, despite these problems, the catalytic poly-
merization by soluble transition metal complexes
via coordination mechanism has been the choice of
preference since by this method a number of reaction
parameters can be introduced. Initial efforts in-
cluded the use of various Ziegler-Natta type
catalysts2' since 1958 when Natta reported the po-
lymerization of acetylene to linear polymer for the
first time.3s In 1974, MasudaZ4investigated the po-
lymerization of phenylacetylene by group 6 metal
halides such as WCI6 or MoC15providing almost se-
lective benzene-soluble yet methanol-insoluble high
molecular weight polymer. The molecular weight of
polymers thus obtained was 5000-15,000. The same
author subsequently reported that the choice of
proper solvent could significantly increase the mo-
lecular weight of the product up to 100,000.28The
catalytic system employed for this study was WC16/

2377
2378 LEE, SHIM, AND KIM

e P
&pph2&
P h 2 qNMe,
PPhz
wN3-o
palladium and nickel c0mplexes,4~and carboxylation
of amines by iron complexes.45
This article describes the synthesis of some new
R h and Ir complexes of ferrocene-based ligands and
DPPF FcNP FcNN their catalytic activity in the polymerization of
Scheme 1. phenylacetylene (Scheme 1).

Ph4Sn (1 : 1) and light-activated W(CO)6. In 1986, EX PER1MENTAL

F ~ r l a n ireported
~~ that the cationic rhodium(1)
complexes of the type [Rh(COD)(Chel)]PF, (COD
= cis,cis-cycloocta-l,5-diene; Chel = 2,2'-bipyridine,
1,lO-phenanthroline, 2,9-dimethyl-l,10 phenanthro-
line, etc.) and the transition metal phosphine com-
plexes such as [Pt (q1-phenylacetyleny 1) (PPh3)2]
revealed the catalytic activity for the highly ster-
eoregular polymerization of phenylacetylene. Un-
fortunately, however, the molecular weights of the
polymers thus obtained were not high (ca. 9000).
More recently, A l ~ e examined
r ~ ~
-
polymerization of
phenylacetylene catalyzed by zwitterionic rhod-
ium(1) complex, Rh+(COD)BPh;, under hydrosila-
tion conditions to give stereoregular cis-PPA with
molecular weight of up t o 35,000. Even more sig-
nificant achievement has recently been reported by
Tabata e t al. that a n ultrahigh-molecular weight
P P A (Mwca. 4.30 X lo6) can be obtained by a Rh(1)
complex such as [Rh(norb~rnadiene)Cl]~.~~,~~
These findings have led us to investigate the
reactivity of some rhodium and iridium complexes
incorporating ferrocene-based organometallic li-
gands for the polymerization of phenylacetylene,
since complexes of ferrocenylamines or ferrocenyl-
phosphines have found applications a s catalyst and
reagent in a variety of homogeneous catalysis and
asymmetric synthesis. Some representative exam-
ples are hydrogenation of olefins by rhodium com-
ple~es,~ hydrosilation
~-~~ of ketones by platinum
complexes,43 Grignard cross-coupling reactions by
lnstrumentals and Materials
All manipulations were carried out under a n argon
atmosphere using a double manifold vacuum system
and Schlenk techniques. All commercial reagents
were used as received unless otherwise mentioned.
Phenylacetylene was distilled over calcium hydride
before use. Solvents were purified by standard
methods, and were freshly distilled prior t o use. Mi-
croanalyses were performed by The Center for In-
strumental Analysis, Kyungpook National Univer-
sity. 'H-, and 3'P-NMR spectra were recorded
on a Bruker AM-300 spectrometer operating a t 300,
80.15, and 121.5 MHz, respectively. IR spectra were
recorded on a Mattson FT-IR Galaxy 6030 E Spec-
trophotometer with KBr pellets. Gel permeation
chromatograms (GPC) were measured by using a
Waters 510 M liquid chromatography apparatus
containing Ultra Styragel linear and Styragel H R
columns, and a n M 410 RI detector. Based on the
GPC curves number- and weight-average molecular
weights were tentatively calculated using a calibra-
tion curve for polystyrene standards. GC-mass
spectra were obtained by using a Shimadzu QP-1000.
Thermogravimetric analysis (TGA) and differential
scanning calorimeter (DSC) were performed by a
PL-STA model 1500 H thermogram, with a heating
rate of 10"C/min in the temperature range of 20-
600°C under a nitrogen atmosphere. UV and visible

Table I. Physical and Analytical Data for Rh and Ir Complexes"

Analysis
mPb
Compound ("C) c (%) H (%I N (%)

[Rh(DPPF)(COD)]ClO, 210 57.82 (58.32) 4.14 (4.68) -

[Rh(FcNP)(COD)]C104 180 53.78 (54.10) 5.03 (4.54) 1.91 (1.91)

[ Rh(FcNN)(COD)]ClO, 192 50.52 (50.39) 5.31 (4.76) 3.27 (3.76)
[ Rh(FcNN)Cl], 196 49.46 (48.82) 4.60 (4.10) 4.22 (4.74)
[Ir(DPPF)(COD)]ClO, 270 49.85 (50.46) 4.02 (4.03) -
[Ir(FcNP)(COD)]ClO, 250 53.10 (53.72) 5.75 (5.19) 2.31 (1.90)
[ Ir(FcNN) (COD)]ClO, 260 44.63 (45.11) 4.45 (4.26) 3.25 (3.29)

Values in parentheses are calculated ones

Decomposition temperature.
 CATALYTIC POLYMERIZATION OF PHENYLACETYLENE 2379

Table 11. 'H- and 31P-NMRData for Rh and Ir Complexes"

Complex 'H 3'P

[Rh(DPPF)(COD)]CIO, 2.14-2.41 (m, 8 H, CH,), 4.27, 4.35 (A2B2,8 H, C5H4),4.41 22.76

( s , 4 H, CH=CH), 7.59-7.69 (m, 20 H, phenyl)

[Rh(FcNP)(COD)]C104 1.97-2.73 (m, 8 H, CH,), 2.50 ( s , 6 H, NMe,), 3.31 (9, 2 H, CH,,

JHH = 13 Hz), 3.67 (s, 5 H, C5H5),4.21-4.39 (m, ABC, C5H3),
4.63 (s, 4 H, CH=CH), 7.23-7.79 (m, 10 H, phenyl)

[Rh(FcNN)(COD)]ClO,
[Rh(FcNN)CI],
[Ir(DPPF) (COD)]C104
[Ir(FcNP)(COD)]C104
[ Ir(FcNN)(COD)]ClO,
2.06, 2.61 (AB, 8 H, CH,), 3.81, 4.14, 4.31 (AzB2, 4 H, CHp), 4.24
( s , 4 H, CH=CH), 4.35 (s, 10 H, C5H5),4.71, 4.78 (A,B2, 8 H,
C5H4), 7.42 (s, 2 H, N=CH)
3.70, 4.21 (AB, 4 H, CHJ, 4.35 (s, 10 H, C5H5), 4.68, 4.78 (ApBp,
8 H, C5H4),9.96 (s, 2 H, N=CH)
1.67-2.22 (8 H, CHp), 4.07 (s, 4 H, CH=CH), 4.30, 4.38 (A2B2, 15.28 ( s )
8 H, C5H4),7.60-7.79 (m, 20 H, phenyl)
1.66-2.31 (8 H, CH,), 2.51 (s, 6 H, NMe,), 3.04 ( s , 4 H, 10.36
CH=CH), 3.67 (s, 5 H, C5H5), 3.77 (9, 2 H, CHp, JHH = 13 Hz),
4.32-4.57 (m, ABC, C5H3),7.21-7.77 (m, 10 H, phenyl)
1.75-2.61 (8 H, CH,), 4.34 (s, 10 H, C5H5),4.17, 4.36 (4 H, CH,),
4.40 (s, 4 H, CH=CH), 4.61, 4.68 (A2B2,8 H, C5H4),9.96
(s, 2 H, N=CH)

a All spectra were obtained in CDC1,. Coupling constants are in Hz: s = singlet; d = doublet; q = quartet; m = multiplet.

spectra were measured in dichloromethane on a
Shimadzu UV-2100 spectrophotometer. Melting
points were determined using a Thomas-Hoover
melting point apparatus and reported without cor-
rection.
T h e ligands DPPF46and F c N P , ~were prepared
according to the literature methods.
Synthesis of 1,6-Diferrocenyl-2,5-diazahexane
(FcNN)
T o a n orange-red solution of ferrocenecarboxalde-
hyde (0.43 g, 2 mmol) in ether (10 mL) were added
MgS04 (0.2 g, 1.9 mmol) and a solution of half molar
amount of ethylenediamine in ether ( 5 mL). T h e
reaction mixture was stirred a t room temperature
for 18-24 h. T h e resulting solution was filtered and
the filtrate was evaporated to dryness under reduced
pressure. The orange residue was redissolved in ether
and the solution was cooled t o 0°C t o give yellow
crystalline solid (70% yield).
Synthesis of [Rh(LL)(COD)]CIO, (11 = DPPF,
FcNP, FcNN)
In a typical e~periment,~'.~'
a n acetone solution of
NaC10, (0.06 g, 0.46 mmol) was added t o a n orange
solution of [Rh(COD)Cl], (0.15 g, 0.22 mmol) in
acetone. After removing NaCl by filtration, the fil-
trate was refluxed for 30 min a n d treated with a
solution of LL (0.46 mmol) in toluene. The resulting
red solution was further stirred a t room temperature
for about 3 h. Solvents were removed in uacuo, and
the resulting dark-red solid was redissolved in ace-
tone for crystallization to give red crystals (54-68%
yield).
Synthesis of [Rh( FcN N)CI],
T h e title compound was prepared according to the
literature procedure^.^",^^ [Rh(COD)Cl], (0.15 g, 0.22
mmol) was dissolved in toluene in a Schlenk tube.
T o the stirred solution was added FcNN (0.22 g,
0.48 mmol) in toluene. T h e solution was further
stirred for 24 h during which time a fine orange pre-
cipitate deposited. This was isolated on a Schlenk
filter, washed with diethylether, and dried (42%
yield).
Synthesis of [Ir(LL)(COD)]ClO, (11 = DPPF, FcNP,
FCNN)'',~'
In a typical experiment a n acetone solution of
NaC10, (0.06 g, 0.52 mmol) was added to a n orange
solution of [Ir(COD)Cl], (0.15 g, 0.24 mmol) in ace-
tone. After removing NaCl by filtration, the filtrate
was refluxed for 30 min and treated with a solution
of ligand (0.46 mmol) in toluene. T h e resulting red
solution was further stirred a t room temperature for
30 min. Solvents were removed in uacuo, and the
2380 LEE, SHIM, AND KIM

Figure 1. 'H-NMR spectrum of [(COD)Rh(FcNN)]ClO,.

resulting dark-red solid redissolved in cyclohexane/ Scheme 1 are described e l ~ e w h e r e , ~ ~

and
. ~ ~have
*~*
dichloromethane for crystallization (51-65% yield). been employed with slight modification in the pres-
ent studies. In particular, we have recently developed
Catalytic Polymerization of Phenylacetylene excellent routes t o the formation of the ferrocenyl
Schiff base, FcNN, as represented in eq. (1):
T o a 25 mL round-bottom flask charged with
phenylacetylene (0.60 mL, 5.44 mmol) in a solvent A
(- 15 mL) was added the catalyst (0.02 mmol).
T h e reaction mixture was stirred for 24 h a t room
temperature. T h e yellow precipitates of polyphe-
nylacetylene which were formed during the reac-
tion period were filtered, washed with methanol,
and dried in uacuo. (i) MgSO, / ether / RT / 24 h
(ii) RuCI,(PPh,), / dioxane / RT / 5 h

RESULTS AND DISCUSSION Equation (1) shows that it can be obtained either
in the presence of MgSO, or catalytically by the ac-
Ligand and Complex Formation tion of R U C ~ ~ ( P PThe ~ ~latter
) ~ . afforded quanti-
The preparative methods for the ferrocene-contain- tative yield. These methods were extended to fer-
ing chelate ligands such as those illustrated in rocene- 1,l'-dicarboxaldehyde for the preparation of
polyazamacr~cycles.~~
These ligands form the cationic rhodium and
iridium complexes of the type [ M(LL)(COD)]C104
/ \ 1 \ (M = Rh, Ir; COD = cyclooctadiene; LL = DPPF,
Ph HPh HPh HPh
FcNP, FcNN) by replacing 2 equiv of solvent from
Ph H O ~ , is formed in situ
[ M ( C O D ) ( ~ o l v e n t ) ~ ] C lwhich
0s-asoidal PPA (A) os-transo/dal PPA (B) trans-oso&l PPA (C) from the reaction of [MCl(COD)], with 2 equiv of
Scheme 2. NaC10, in acetone [eq. (2)]:
 CATALYTIC POLYMERIZATION OF PHENYLACETYLENE 2381

Table 111. Polymerization of Phenylacetylene with Rh/Ir Complexes"

Softening
Yieldb Temperature cis Content'
Catalyst Ligand (%) M n M u MwlMn ("(2) (So)

[Rh(LL)COD]ClO, FcNN 94 33,340 85,850 2.5 202-220 99.35

FcNP 92 30,790 76,910 2.5 214-228 92.91
DPPE 76 33,200 94,740 2.8 203-216 95.80
DPPF 74 19,740 47,970 2.4 203-212 94.02
[Rh(LL)Cll, DPPF 61 33,490 145,270 4.3 211-222 96.71
FcNN 68 33,400 140,760 4.1 207-218 97.21
[Ir(LL)COD]C104 FcNN 28 940 1780 1.9 171-1 79 92.30
FcNP 22 920 1460 1.6 171-178 91.07
DPPF 18 800 1760 2.2 173- 179 92.12

Reaction Conditions: [catalyst] = 0.3 mol % in methanol (15 mL); reaction time = 24 h a t room temperature.
Isolated yield.
' Calculated according to Reference 21.

[M(COD)Cl],+ 2LL + 2NaCI0, -zC,

P[M(COD)(LL)]CIO,
All these complexes have been characterized by
microanalysis and NMR. The results are provided
in Tables I and 11. The most characteristic feature
of the 'H NMR spectra of the complexes is the pres-
ence of various Cp ring patterns. In general, the
monosubstituted Cp ring is known to exhibit an AB
doublet or a broad singlet on a 'H-NMR spectrum
depending upon the type of the c ~ m p l e x . ~For
' ex-
ample, the ligand DPPF in [Rh(DPPF)(COD)]ClO,
exhibits a typical AB quartet due to the symmetri-
cally monosubstituted Cp rings, while the FcNN li-
gand in the same type of complex gives rise to a pair
of singlets (6 = 4.71 and 4.78 ppm) due to the mono-
substituted Cp rings in addition to a sharp singlet
(6 = 4.35 ppm) from the unsubstituted Cp rings as
can be seen in Figure 1. Other interesting features
concerning the FcNN ligand is that the methylene
protons of the ethylenediamine moiety shows a pair
of singlets in the free ligand (6 = 3.76 and 4.19
~ p m ) : while
~ the singlet at 4.19 ppm splits into two
lines (6 = 4.14 and 4.31 ppm) in the complex. This
splitting may be ascribed to the fact that their rel-
ative positions are rather fixed in the space through
coordination. Also interesting is the fact that the
imine signal moves to a higher field upon complex-
ation to 7.42 ppm in the complex from 8.16 ppm.
The COD ligand exhibits the expected patterns giv-
ing rise to a singlet due to the vinyl protons in the
4.2-4.6 ppm region and an AB quartet due to the
methylene protons in the 1.6-2.6 ppm region.
The 31P-NMRpattern is quite straightforward;
thus the ligand DPPF and FcNP giving the expected
doublets at 22.76 and 18.43 ppm, respectively, due
to the coupling with rhodium ('03Rh: I = $; 100%
(2) natural abundance). The coupling is larger with
FcNP.
Catalytic Polymerization of Phenylacetylene
As mentioned previously catalytic polymerization
of phenylacetylene by transition metal complexes is
well established [eq. (3)]:
The product, polyphenylacetylene (PPA), thus
obtained in this reaction can in principle exist as
one or a mixture of three possible stereoisomeric
forms shown in Scheme 2 . Here the first cis-/trans-
denotes the configuration around the olefinic double
bond, and the second cisoidal/transoidal refers to the
direction of chain growth along the single bond con-
necting the acetylenic unit. As each isomer has its
unique physicochemical and spectroscopic proper-
ties, their separation from the reaction mixture as
well as characterization can be easily achieved. For
instance, the cis-cisoidal-PPA can be separated from
the other two isomers, cis-transoidal-PPA and
trans-cisoidal-PPA according to their solubility in
benzene: the latter two are soluble in benzene while
the former is not. The benzene-soluble isomers can
be identified by spectroscopic techniques such as 'H-
NMR and IR, and the ratio of their relative amount
in solution obtained.
The most striking differences in the IR pattern
among the three isomers is the presence of the
C -H out-of-the-plane stretching band a t 740 cm-'
due to cis-cisoidal-PPA and cis-transoidal-PPA and,
a t the same time, the absence of the band a t 1265
2382 LEE, SHIM, AND KIM

7.5

144 142 140 138 136 134 132 in 118 186

Figure 2. Typical 'H- and "C-NMR spectra of cis-PPA obtained with [(COD)-
Rh(FcNN)]ClO,.

cm-', while the trans-cisoidal isomer shows quite the
opposite behavior with the band at 740 cm-' lack-
ing and the one a t 1265 cm-' revealing. The ab-
sorptions at 740 and 1265 cm-' are thus a function
of the cis and the trans contents, respectively, in the
polymer.
T h e use of 'H-NMR is also helpful. Namely, in
addition to the chemical shift differences of aro-
matic protons, the peak a t 5.82 ppm due to the
olefinic proton is the characteristic features of the
cis-transoidal and cis-cisoidal isomers only. The
area of this peak may be correlated with the in-
tensity of the band a t 740 cm-' and can be em-
ployed to determine the cis content in the product
mixture according to the Simionescu equation2'
shown below:
 CATALYTIC POLYMERIZATION OF PHENYLACETYLENE 2383

100

--
M 80
u
m
C
2 60
E
a

,
40

20

3000 2503 2000 1500 1000 500

Wavc.iurnbers ( c m - ' )
0 100 200 300 400 500 600
Figure 3. Typical IR spectrum of cis-PPA obtained with
[(COD)Rh(FcNN)]ClO,. Temperature ('C)

Figure 4. TGA and DSC graph of cis-PPA obtained

% cis = (A5,82
X 104)/(A,X 16.66) with [(COD)Rh(FcNN)]ClO,.

where A5,82and A , are the areas for the signal a t 5.82

(a,
ppm and the whole signals, respectively. It is now
well known that the formation as well as the relative
-
namely, it gives the highest molecular weight
33,000), the highest chemical yield (94%), the
highest stereoregularity (99.35% of cis-transoidal-
amount of each isomer in the product is the function
PPA), and the lowest polydispersity (M,/I@,, = 2.5).
of various parameters such as the central metal, the
The same trend is also maintained with the bime-
ligand, solvent, and the reaction temperature.
tallic rhodium complexes as well as the cationic
For instance, Kern,IgBerlin,gand S i m i o n e s c ~ ~ ~ . ~ ~
iridium complexes, [ (COD)Ir(LL)]ClO,. Iridium
reported that the Ziegler-Natta-type catalysts such
as AlH(i - Bu)/Fe(acac), (acac = acetylacetone),
A1Et,/TiCl3, and A1Et3/Fe(dmg), 2Py (dmg = di- -
methylglioxime) yielded mainly cis-transoidal-PPA H I

and that cis-cisoidal-PPA could also be obtained as

a benzene-insoluble crystalline fraction with the last
two catalysts. Other Ziegler-Natta catalysts such as
A1Et3/TiC14,and A1Et3/M(acac), were reported t o
give trans-cisoidal-PPA.22
Prompted by these findings, we have employed
our new rhodium and iridium complexes of ferro- h'
-
cenyl ligands a s catalyst in the formation of PPA. "
u
l4O0C
v
1I
a
T h e results are summarized in Table 111, and the *
C
.- -2

table shows t h a t the cationic rhodium complexes, 5

[ (COD)Rh(LL)]ClO,, and the neutral bimetallic a
F &.
complexes, [Rh(LL)Cl],, are very effective cata-
lysts to give highly stereoregular polyphenylacety-
lenes with high molecular weights and low polydis-
persity (&?,/@,) in high yields under mild condi-
tions. In particular, the cationic rhodium complexes,
[ (COD)Rh(LL)]ClO,, gives almost exclusively cis-
transoidal-PPA with product yields that are among
the highest reported in the literature. Of the two
types of complexes, the mononuclear cationic sys-
tems reveal much better efficiency in every respect
2000 1500 1000 500
except one t h a t the bimetallic complexes give P P A
Wavenumbers ( c m - ' )
with higher M , values.
T h e table also shows that the chelate diimine Figure 5. Variable temperature IR spectra of cis-PPA
(FcNN) is the best among the four ligands employed obtained with [(COD)Rh(DPPF)]ClO,.
2384 LEE, SHIM, AND KIM

Table IV. Influence of the Relative Amount of Catalyst

Softening
[Catalyst]/[Monomer] Yield' Temperature
(mol %) (%) Mn a"> MJMn ("C)

0.3" 68 8660 21,190 2.4 172-178

1.on 90 7110 7850 1.2 183- 195
3.0" 88 3510 4640 1.3 187-196
0.03b 52 35,450 101,870 2.8 214-228
0.3b 94 30,790 76,910 2.5 208-219
1.0b 99 13,750 26,130 1.9 204-214

Catalyst = [Rh(DPPF)(COD)]CIO, a t room temperature for 24 h in chloroform.

Catalyst = [Rh(FcNP)(COD)]ClO, a t room temperature for 24 h in methanol.
' Isolated yield.

complexes have proven to be poor catalyst in that
they give low-molecular weight PPA in low yields.
In fact, it was observed that catalytic trimerization
is the favored course of reaction with these com-
plexes.
Figure 2 shows the typical 'H- a n d 13C-
N M R spectra of a P P A sample obtained with
[Rh(FcNN)(COD)]ClO,. It can be seen that they
are in good agreement with that of stereoregular po-
lyphenylacetylene having a cis-transoidal structure.'
T h e IR spectrum of the same P P A shown in Figure
3 suggests that the polymerization product be a lin-
ear polymer with a polyene structure.'
Thermogravimetric analysis (Fig. 4) shows that
the polymer is stable up t o 280°C in a n atmosphere
of nitrogen. Complete decomposition occurs between
280 and 550"C, a t a rate of about 3% for every 50°C
increase in temperatures between 300 and 500"C,
and then the residual reached 8% at 550°C. The
DSC thermogram in the figure shows three peaks
typical for cis-polyacetylene, but no inflection cor-
responding to the glass transition is observed. The
first exotherm observed in the cis polymer has a
maximum a t 189°C. Another exothermic peak is ob-
served a t 259°C. According to Kleist and B ~ r d ,the
~,
two exotherms correspond to cis-trans isomerization
and crystallization phenomena, respectively. The
endothermic peak a t around 300°C is characteristic
of thermal decomposition of the cis polymers.
The variable temperature IR spectra of the same
PPA sample obtained with [Rh(DPPF)(COD)]ClO,
show quite consistent behaviors with these obser-
vations as demonstrated in Figure 5 . Thus, for ex-
ample, i t can be observed that on raising the tem-
perature, the two bands a t 740 and 895 cm-' dimin-
ish with concomitant appearance of a new band a t
1265 cm-I. Each spectrum was obtained with the
solid sample of PPA warmed a t the specified tem-
perature for 30 min.
T h e relative amount of catalyst plays a role on
the yields of the polymer as well as the molecular
weight. Thus, Table IV shows that regardless the
ligands employed, the chemical yields reach the
maxima when [Cat.]/[Monomer] is 1.0 mol %. The
molecular weights, on the other hand, increase with
the decrease in the catalyst concentration.

Table V. Influence of Solvents on Polymerization of Phenylacetylene by [ Rh(LL)COD]C104'

Softening
Yieldb Temperature cis Content'
LL Solvent (%) M" M w Mu,/Mn ("C) (%I
FcNN Methanol 94 33,340 85,850 2.5 202-220 99.35
Dioxane 67 24,890 120,930 4.9 200-219 97.24
Chloroform 90 22,350 93,190 4.2 186-195 < 40
Benzene 78 2500 5130 2.1 172-180 < 40
DPPF Methanol 74 19,740 47,970 2.4 203-212 94.02
Chloroform 68 8660 21,190 2.4 172-178 57.09
Benzene 25 1050 1540 1.5 171-177 i40

a [Catalyst] = 0.3 mol 96; reaction time = 24 h; temperature = RT.

Isolated yield.
Calculated according to Reference 21.
 CATALYTIC POLYMERIZATION OF PHENYLACETYLENE 2385

Table VI. Influence of Reaction Temperature on Polymerization of Phenylacetylene by [Rh(LL)COD]ClO,''

Softening
T Yieldb Temperature cis Content'
LL ("C) (%) M, M u Mumn ("C) (%)

FcNN 65 73 11,400 49,530 4.3 202-212 98.56

30 94 33,340 85,850 2.5 202-220 99.35
0 41 12,220 108,680 8.9 198-210 97.96
DPPF 65 56 28,450 86,160 3.0 206-217 94.38
30 74 19,740 47,970 2.4 203-212 94.02
0 28 8540 44,410 5.2 193-200 93.39

* [Catalyst] = 0.3 mol %; reaction time = 24 h; solvent = MeOH

Isolated yield.
' Calculated according to Reference 21.

Methanol is the preferred solvent in every respect REFERENCES AND N O T E S

as can be seen from Table V. The table shows the
significant reduction in the cis content in other sol-
vents. Finally, Table VI shows the influence of re-
action temperature on the polymerization. The best
results are obtained at ambient temperature under
the standard set of reaction conditions.
Although we have made no attempts to illuci-
date the mechanism of polymerization by our sys-
tem, linear polymerization of phenylacetylene may
occur by at least two different pathway^^^-^^: (1)
the four-center acetylene insertion mechanism,
and ( 2 ) the metallacycle mechanism. The former
route should involve initially the oxidative addi-
tion of phenyacetylene to the disolvato complex,
[Rh(LL) (solvent)z+],formed by probably dissocia-
tion of COD from the precursor, to give the hydri-
doacetylenic complex. Coordination followed by mi-
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rhodium intermediate which will lead eventually to
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rangement of one PA in the diacetylenic complex57
that is generated by stepwise coordination of 2 equiv
of P A to [Rh(LL)]+.This, in turn, may give a me-
tallacycle through 1,2-addition. Repetition of these
processes eventually yields the PPA.
We thank the Korea Science and Engineering Foundation
and the Ministry of Education (BSRI-94-3403) for the
financial support.
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Received April 13, 1995
Accepted January 29, 1996