Macromolecules 1998, 31, 2779-2783 2779

Living Coordination Polymerization of Alkoxyallenes by π-Allylnickel

Catalyst. 2.1 Effect of Anionic Ligands on Polymerization Behavior and
Polymer Structure
Koji Takagi,† Ikuyoshi Tomita,‡ Yoshiyuki Nakamura,† and Takeshi Endo*,†
Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta 4259,
Midori-ku, Yokohama, 226-8503 Japan, and Department of Electronic Chemistry, Interdisciplinary
Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta 4259,
Midori-ku, Yokohama, 226-8502 Japan
Received November 28, 1997; Revised Manuscript Received March 4, 1998

ABSTRACT: The coordination polymerization of (n-octyloxy)allene (2) was carried out by π-allylnickel
catalysts possessing various carboxylate ligands (1a-1c). The electronic character of the carboxylate
ligand strongly influences the polymerization. Electron-withdrawing groups provide a living system that
produces polymers with well-defined molecular weights and narrow molecular weight distributions in
high yields. Without electron-withdrawing substituents, the reaction produces oligomeric byproducts.
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The ratio of 1,2- to 2,3-polymerization unit in the polymer increased with the electron-withdrawing
character of carboxylate ligands. π-Allylnickel catalysts bearing halide ligands (1d, 1e, and 1f/Na2S2O3)
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also gave polymers from 2 in high yields, in which the polymerization rate, the microstructure, and the
molecular weight distributions (Mw/Mn) of polymers were dependent upon the specific halide. The catalyst
with chloride (1d) afforded a polymer with narrow Mw/Mn (1.03), possessing the ratio of 1,2- to
2,3-polymerization unit of 6:94, whereas with iodide (1f/Na2S2O3), the polymerization took place much
faster to give a polymer (1,2-:2,3-polymerization unit ) 16:84) with a little broader Mw/Mn (1.10).

Introduction Scheme 1
The living polymerization technique is a most promis-
ing route to obtain well-defined polymers with predict-
able molecular weights and narrow molecular weight
distributions. Block copolymers, telechelic polymers,
macromonomers, star-shaped polymers, etc. can be
designed on the basis of living systems.
Transition metal-catalyzed polymerizations of sub-
stituted acetylenes,2 cyclic olefins,3 R,ω-dienes,4 conju-
gated dienes,5 and heterocumulenes6 can be controlled
by the structural modification of the initiating system. Scheme 2
Polymerization rates and polymer microstructures can
be systematically controlled by the catalyst structure
(e.g., the valence state of the metallic center and the
electronic and/or the steric feature of the ligated sys-
tem). For instance, in the coordination polymerization
of 1,3-butadiene by π-allylnickel carboxylates, electron-
withdrawing carboxylate ligands have been reported to
influence the polymerization rate of 1,3-butadiene.7 The
addition of electron acceptors such as hexafluoroacetone
to π-allylnickel trifluoroacetate also promotes the cata-
lytic activity in the polymerization of isocyanides.8
Recently, we have reported the living coordination
polymerization of alkoxyallenes by the [(π-allyl)NiO-
COCF3]2/PPh3 system, where the polymerization pro-
ceeds under mild conditions to give polymers with sufficiently to give polymers in low yields.10 To clarify
narrow molecular weight distributions (Mw/Mn < 1.1) the effect of ligated systems on the polymerization
and controlled molecular weights9 (Scheme 1). behavior and to design the precise polymerization
The allylnickel catalyst, [(allyl)Ni(X)L], possesses both system for allene derivatives, we report the coordination
anionic (X) and neutral (L) ligands, which may influence polymerization of (n-octyloxy)allene (2) by π-allylnickel
the polymerization behavior of alkoxyallenes. Although catalysts having various anionic ligands (1a-1e and 1f/
the effect of the ligand character on the polymerization Na2S2O3) (Scheme 2).
rate and the polymer structure has been discussed in
the coordination polymerization of alkylallene by π-al- Results and Discussion
lylnickel halides, the polymerization does not proceed Coordination Polymerization of (n-Octyloxy)-
allene (2) by π-Allylnickel Catalyst Bearing Car-
† Research Laboratory of Resources Utilization. boxylate Ligands (1a-1c). Allylnickel carboxylates
‡ Department of Electronic Chemistry. are accessible by the oxidative addition of Ni(0), from
S0024-9297(97)01740-3 CCC: $15.00 © 1998 American Chemical Society
Published on Web 04/17/1998
2780 Takagi et al.
Figure 1. GPC profiles of poly(2) produced by the polymerization of 50 equiv of 2 by 1 and those obtained by the further reaction
of 50 equiv of 2, where two sets of the experiments were made by 1c (a) and 1a (b) as a catalyst, respectively. GPC profile of
poly(2) obtained by 1c kept for 1 h under nitrogen at ambient temperature before the polymerization (c).
bis(1,5-cyclooctadiene)nickel (Ni(cod)2), with allyl car-
boxylates.11,12 On the basis of some of these complexes
with different substituents on carboxylate moieties,
PPh3 (2 equiv, relative to the nickel) was added, and
the complexes thus obtained (1a-1c) were used as
catalysts for the coordination polymerization. In our
earlier work,9 the [(π-allyl)NiOCOCF3]2/PPh3 system
was reported to give polymers which are soluble in
organic solvents and consisting of both 1,2- and 2,3-
polymerization units in the ratio 23:77. On the other
hand, by using the [(π-allyl)NiOCOCF3]2 system (with-
out PPh3), polymers of methoxyallene and ethoxyallene
were barely soluble, but those of allenyl ethers bearing
longer aliphatic chains (e.g., n-butoxyallene and (n-
octyloxy)allene) were soluble in organic solvents and
predominantly consist of 2,3-polymerization units. To
avoid the formation of less soluble polymers in the
systematic study of the catalyst system, a monomer
bearing long aliphatic chains (e.g., n-octyloxyallene, 2)
was used.
When the polymerization of 2 (50 equiv) was carried
out from 0 °C to ambient temperature in toluene, the
reaction was complete within 12 h in a homogeneous
solution, independent of the catalysts used. However,
clear differences were observed in polymer yields and
microstructures by varying the character of the car-
boxylate ligands. Although the catalyst bearing a CF3
group having the electron-withdrawing character on the
carboxylate ligand (1a), which is known as a stable
π-allylnickel complex, yielded a polymer (Mn ) 8710)
quantitatively with a very narrow molecular weight
distribution (Mw/Mn ) 1.03) (Table 1, run 1), those not
possessing sufficient electron-withdrawing carboxylate
ligands (1b and 1c) afforded products consisting of
bimodal molecular weight distributions by GPC analy-
ses (e.g., a polymer obtained by 1c was composed of a
higher molecular weight fraction, Mn ) 8060, Mw/Mn )
1.02 (61%), and a lower molecular weight fraction, Mn
) 2520, Mw/Mn ) 1.04 (38%)). The double bonds in
polymers obtained by 1a-1c were detected quantita-
tively, as expected from 1,2- and 2,3-polymerization by
1H NMR spectra, in which the ratio of the 1,2- to 2,3-
polymerization unit increased with the electron-with-
drawing character of carboxylate ligands. That is, the
content of the 1,2-polymerization unit in poly(2) pre-
pared by 1a was 22%, while that obtained by 1c
decreased to 5%.
Macromolecules, Vol. 31, No. 9, 1998
Table 1. Coordination Polymerization of 2 by
π-Allylnickel Catalysts (1a-1c)a
run R yield (%)b Mnc Mw/Mnc unit ratio (%)d
1 CF3 (1a) 99 8710 1.03 22:78
2 CH2Cl (1b) 97e 6570 1.12 8:92
3 CH3 (1c) 99f 5380 1.30 5:95
a Conditions: [1] ) 2.0 × 10-2 mmol, [2] /[Ni] ) 50, at 0 °C f
0
room temperature, for 12 h, in toluene. b Isolated yield after
precipitation into MeOH/H2O (v/v ) 1/1). c Estimated by GPC
(THF, PSt standard). d Determined by 1H NMR spectra of the
isolated polymers. e Products contained higher (Mn ) 8460, Mw/
Mn ) 1.03) and lower (Mn ) 2260, Mw/Mn ) 1.04) molecular weight
fractions in 85% and 12% yields, respectively. f Products contained
higher (Mn ) 8060, Mw/Mn ) 1.02) and lower (Mn ) 2520, Mw/Mn
) 1.04) molecular weight fractions in 61% and 38% yields,
respectively.
To clarify reasons for the bimodal molecular weight
distribution in cases of 1b and 1c, additional experi-
ments were carried out as follows: after the complete
consumption of 2 (50 equiv) by 1c, the polymer solution
was kept for 12 h at ambient temperature under
nitrogen, to which 2 (50 equiv) was added again to carry
out the further reaction for 12 h. Although the second
fed monomer was consumed completely, GPC curves of
the polymer indicated multimodal peaks, in which a
shoulder peak was observed in the same molecular
weight region as that of the main product at the first
stage (Figure 1a). Accordingly, a part of the propagating
end produced at the first stage was deactivated before
the second monomer addition.13 In sharp contrast to
this, when the same experiment was carried out by 1a,
the molecular weight of the polymer obtained at the
second stage (Mn ) 16000, Mw/Mn ) 1.04) shifted
completely to the higher molecular weight region com-
pared with that obtained at the first stage (Mn ) 8550,
Mw/Mn ) 1.03), as reported previously using methoxy-
allene9 (Figure 1b).
Likewise, the preparative condition of 1c was found
to influence the polymerization behavior. When the
catalyst (1c) was kept for 1 h at ambient temperature
under nitrogen after the catalyst preparation and the
polymerization was conducted, a polymer (Mn ) 10 000,
Mw/Mn ) 1.07) was obtained in significantly lower yield
(18%) (Figure 1c). According to the previous report, the
complex (1c) decomposes into bis(π-allyl)nickel(II)14 and
nickel(II) acetate by the disproportionation,15 which
might be concerned with the oligomerization process.
Macromolecules, Vol. 31, No. 9, 1998
Scheme 3
Table 2. Coordination Polymerization of 2 by
π-Allylnickel Catalysts (1d-1f)a
run X yield (%)b Mnc Mw/Mnc unit ratio (%)d
1 Cl (1d) 96 8730 1.03 6:94
2 Br (1e) 98 8370 1.05 14:86
3e I (1f) 99 7450 1.10 16:84
4 I 97 6740 1.29 7:93
a Conditions: [1] ) 2.0 × 10-2
mmol, [2]0/[Ni] ) 50, at 0 °C f
room temperature, for 12 h, in toluene. b Isolated yield of the
polymer after precipitation into MeOH/H2O (v/v ) 1/1). c Esti-
mated by GPC (THF, PSt standard). d Determined by 1H NMR
spectra of the produced polymer. e Polymerization was carried out
in the presence of sodium thiosulfate.
Although no reaction took place when 2 and nickel(II)
acetate tetrahydrate were exposed to the same condi-
tions, the reaction of 2 with bis(π-allyl)nickel took place
in the presence of PPh3 to afford oligomeric products
(Mn ) 1780, Mw/Mn ) 1.44) in 90% yield. Accordingly,
the disproportionation product of 1c (i.e., bis(π-allyl)-
nickel) most probably catalyzes the competitive oligo-
merization process.
Polymerization rates were examined to estimate the
influence of the ligand character on the polymerization
rate by 1a-1c, although the concentration of objective
propagating species in 1b and 1c may include some
errors. From monomer conversion curves, observed
kinetic coefficients (kobs in -d[2]/dt ) kobs[1][2]) for 1a,
1b, and 1c were evaluated to be 20.6, 5.08, and 4.27
L‚mol-1‚h-1, respectively. These results can be taken
to mean that the polymerization is accelerated by the
electron-withdrawing character of the carboxylate ligand,
most probably due to the decrease of the electron density
on the nickel atom. As reported previously, the poly-
merization of arylallenes16 was accelerated by increas-
ing the electron density of the allene monomers, from
which we proposed the electrophilic character of the
propagating end. The results obtained in this study
may support further this expression. The requirement
of appropriate electron-withdrawing groups on the
carboxylate ligand for the living polymerization may be
proposed to be mainly because of the higher stability of
the initiator and the propagating end.
Coordination Polymerization of 2 by π-Allylnick-
el Catalyst Bearing Halide Ligands (1d-1f). The
polymerization of methoxyallene and ethoxyallene with
π-allylnickel halides has been reported by Ghalamkar-
Moazzam et al., in which the polymerization behavior
was not fully understood because of the barely soluble
character of obtained polymers.17 In contrast, the
coordination polymerization of 2 (50 equiv) by π-al-
lylnickel halides bearing the PPh3 ligand (1d-1f)18 was
complete within 12 h in homogeneous systems, giving
soluble polymers in high yields (Table 2).
From 1H NMR spectra, contents of the 1,2-polymer-
ization unit in polymers were determined to be 6, 14,
and 7% for 1d, 1e, and 1f, respectively (runs 1, 2, and
4). In cases of carboxylate ligands (1a-1c), the increase
of the electron-withdrawing character of the anionic
ligand tends to increase the content of the 1,2-polym-
erization unit. Since the electron-accepting ability of
Alkoxyallene Polymerization by π-Allylnickel 2781
Figure 2. 31P NMR spectra of [(π-allyl)NiX]2 (X ) Cl, Br, and
I) with 0.8 equiv of PPh3 in toluene/benzene-d6 mixture
(measured at 30 °C).
halide ligands coordinated to the nickel(II) has been
reported in the order Cl < Br < I,19 the content of the
1,2-polymerization unit might be expected to be in the
order Cl < Br < I. Although we have done our best to
purify allyl halides used for the catalyst preparation by
distilling them just before use, in particular, the purity
of allyl iodide might not be sufficient enough. By
assuming the contamination of iodine through the
decomposition of allyl iodide, other propagating species
such as B might be taken into consideration, which
might disturb the accurate observation of the 1,2-
polymerization content in the polymer obtained by the
1f system (Scheme 3). To exclude the possibility, the
polymerization was carried out in the presence of a trace
amount of sodium thiosulfate to produce a polymer (Mn
) 7450, Mw/Mn ) 1.10) in 99% yield. It is of notice that
the polymer contained 16% of the 1,2-polymerization
unit and the molecular weight distribution became
much narrower (run 3).20 The electron density on the
nickel atom of the initiating species was estimated by
31P NMR spectra of PPh coordinated to allylnickel
3
halides, where the peaks were observed at 21.0, 22.3,
and 24.5 ppm for X ) Cl, Br, and I, respectively. Thus,
it was confirmed that the nickel atom became more
electron deficient in the order 1d < 1e < 1f, in
accordance with the electron-accepting ability of the
halide ligand (Figure 2), and that the content of the 1,2-
polymerization unit increased in this order.21
The good stability of the propagating end produced
by catalyst systems 1d, 1e, and 1f/Na2S2O3 could be
confirmed by the postpolymerization experiment, simi-
lar to the case of 1a.
Polymerization rates of 2 by 1d, 1e, and 1f/Na2S2O3
were evaluated from monomer conversions followed by
GC after designated reaction periods. In all cases,
monomer conversions agreed with the first-order kinetic
equation: -d[2]/dt ) kobs[1][2], from which observed
kinetic coefficients (kobs) for 1d, 1e, and 1f/Na2S2O3 were
estimated to be 21.6, 24.3, and 57.2 L‚mol-1‚h-1, re-
spectively (Figure 3). Thus, the polymerization rate was
found to increase in the order 1d < 1e < 1f/Na2S2O3 in
accordance with the order of lowering of the electron
density on the nickel atom.22,23
Conclusion
The influence of anionic ligand on the polymerization
behavior of alkoxyallene was examined by catalysts
2782 Takagi et al.
Table 3. Microstructure of Polymers Obtained by 1a-1e and 1f/Na2S2O3 System
peak intensities at δ (ppm)
catalyst 0.85 1.27 1.58 2.30 + 2.52 + 2.83
1a 3.00 10.0 4.00 1.56
1b 3.00 10.0 4.00 1.84
1c 3.00 10.0 4.00 1.90
1d 3.00 10.0 4.00 1.88
1e 3.00 10.0 4.00 1.72
1f/Na2S2O3 3.00 10.0 4.00 1.68
Figure 3. Kinetic plots in the polymerization of 2 using 1 as
an initiator ([2]0 ) 1.0 M, [1] ) 0.025 M).
bearing carboxylate (1a-1c) and halide ligands (1d-
1f). The electron-withdrawing carboxylate ligand en-
hanced the stability of the initiator and the propagating
end to provide a living system and increased the content
of the 1,2-polymerization unit. π-Allylnickel catalysts
having a halide ligand demonstrated the same trend;
i.e., electron-withdrawing iodide increased the poly-
merization rate and the content of the 1,2-polymeriza-
tion unit. The fact that the polymerization of alkoxy-
allene can be accelerated by using a stronger electron-
accepting ligand may suggest that the present poly-
merization system proceeds via the electrophilic reaction
of the propagating π-allylnickel species toward the
allene monomer.
Experimental Section
Materials and Instruments. (n-Octyloxy)allene (2) was
prepared as previously reported24 and was distilled under
reduced pressure prior to use (37 °C/0.45-0.50 mmHg). Allyl
trifluoroacetate, allyl chloroacetate, allyl acetate, allyl chloride,
and allyl bromide were distilled under nitrogen. Allyl iodide
was washed with sodium thiosulfate solution, distilled under
nitrogen, and used instantly for the preparation of 1f. Bis-
(1,5-cyclooctadiene)nickel (Ni(cod)2) was purchased from Cica
Chemical Co. Triphenylphosphine was recrystallized from
dichloromethane/n-hexane. Toluene was dried over sodium
and distilled under nitrogen. All polymerization reactions
were carried out under nitrogen.
1H NMR and 13C NMR spectra were recorded in CDCl on
3
a JEOL EX-400 instrument (400 and 100 MHz, respectively,
tetramethylsilane as an internal standard). 31P NMR spectra
were recorded in a dried and degassed toluene/benzene-d6
mixed solvent under nitrogen on a JEOL FX-100 instrument
(40.5 MHz, 80% aqueous phosphoric acid as an external
standard). IR spectra were obtained on a JASCO FT/IR-5300
spectrometer. Gel permeation chromatographic analyses were
carried out on an HLC-8020 (TSK gel G2500HXL + G3000HXL
and G4000HXL + G5000HXL, THF as an eluent), calibrated
against standard polystyrene samples. Purification by HPLC
was made on a Japan Analytical Industry LC-908 (JAIGEL,
THF as an eluent). Gas chromatographic (GC) analyses were
performed on a Shimadzu GC-14B equipped with an FID
detector using n-tetradecane as an internal standard (SE-30,
3 m, gradient temperature of 100-230 °C, 15 °C/min).
Coordination Polymerization of 2 by 1a (Typical
Procedure). π-Allylnickel complex 1a was prepared from Ni-
Macromolecules, Vol. 31, No. 9, 1998
3.30 3.61 4.00 4.81 + 5.12 5.79 + 5.73 x:y (%)
0.44 1.56 0.22 0.44 0.78 22:78
0.16 1.84 0.08 0.16 0.92 8:92
0.10 1.90 0.05 0.10 0.95 5:95
0.12 1.88 0.06 0.12 0.94 6:94
0.26 1.72 0.14 0.28 0.86 14:86
0.32 1.68 0.16 0.32 0.84 16:84
(cod)2 and an equimolar amount of allyl trifluoroacetate at
ambient temperature under nitrogen11 followed by the addition
of PPh3 (2 equiv, relative to the nickel) and used without
purification. To a flask containing a magnetic stirrer bar and
a toluene solution of 1a (2.0 × 10-2 mmol) was added 2 (0.168
g, 1.00 mmol, 50 equiv) at 0 °C, and the mixture was stirred
for 12 h at ambient temperature. After the complete conver-
sion of 2 was confirmed by GC, the solvent was removed under
reduced pressure and the viscous product was dissolved in
THF (2 mL) and then precipitated into MeOH/H2O (v/v ) 1/1)
(100 mL) to give poly(2) in 99% yield (0.166 g, 0.993 mol): 1H
NMR (CDCl3, δ, ppm) 0.85 (-CH3, 3H), 1.27 (-OCH2CH2-
(CH2)5-, 10H), 1.58 (-OCH2CH2(CH2)5-, 4H), 2.30, 2.52, 2.83
(dCsCH2sCd, 2H × 0.78), 3.30 (>CsOCH2-, 2H × 0.22),
3.61 (dCsOCH2-, 2H × 0.78), 4.00 (>CHsO-, 1H × 0.22),
4.81, 5.12 (dCH2, 2H × 0.22), 5.79, 5.93 (dCHsO-, br, 1H ×
0.78); 13C NMR (CDCl3, δ, ppm) 14.1, 22.7, 25.8, 26.0, 26.4,
29.5, 30.0, 31.9, 32.8, 63.0, 71.8, 114.0, 142.4, 145.8; IR (neat,
cm-1) 2928, 2859, 1664, 1466, 1433, 1377, 1265, 1128.
The other polymerization systems obeyed this protocol, and
polymers were isolated by HPLC separation after precipitating
into MeOH/H2O (v/v ) 1/1) (Table 3).
Estimation of the Kinetic Coefficients. The polymeri-
zation of 2 ([2]0/[1a] ) 40, [2]0 ) 1.0 M, [1a] ) 0.025 M) was
likewise performed in toluene containing n-tetradecane (0.038
M) as an internal standard. After designated reaction periods
at 0 °C, a trace reaction mixture was sampled by the syringe
(ca. 10 µL), and the monomer conversion was estimated by
GC analyses.
Reaction of 2 with Bis(π-allyl)nickel. Bis(π-allyl)nickel
was synthesized by the reaction of NiCl2 (4.37 g, 20 mmol)
with allylmagnesium bromide (48 mmol) in 45% yield accord-
ing to the previously reported procedure.25 To a flask contain-
ing a toluene solution of bis(π-allyl)nickel (0.05 mmol) and
PPh3 (0.10 mmol) was added 2 (1.00 mmol) at 0 °C, and the
reaction mixture was stirred for 12 h at ambient temperature.
By precipitating into MeOH/H2O (v/v ) 1/1), the oligomeric
products (Mn ) 1780, Mw/Mn ) 1.44) were obtained in 90%
yield (1,2-:2,3-polymerization unit ) 30:70).
Supporting Information Available: GPC profiles con-
cerning the stability of the propagating end generated by
π-allylnickel halides (1d, 1e, and 1f/Na2S2O3) (1 page). Order-
ing information is given on any current masthead page.
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(17) Ghalamkar-Moazzam, M.; Jacobs, T. L. J. Polym. Sci., Part
A: Polym. Chem. 1978, 16, 615.
Alkoxyallene Polymerization by π-Allylnickel 2783
(18) Allylic halides are known to react with Ni(cod)2 at or below
0 °C in nonpolar solvents to give dimeric π-allylnickel halides
in almost quantitative yields. Cycloocta-1,5-diene dissociated
from the nickel is reported to be inert toward the formed
complexes. See: (a) Wilke, G. Angew. Chem., Int. Ed. Engl.
1966, 5, 151. (b) Billington, D. C. Chem. Soc. Rev. 1985, 14,
93.
(19) (a) Scholten, J. P.; Play, H. J. Tetrahedron Lett. 1972, 17,
1865. (b) Gray, H. B.; Billig, E.; Wojcicki, A.; Farona, F. Can.
J. Chem. 1963, 41, 1281.
(20) In the cases of 1d and 1e, the addition of sodium thiosulfate
gave no significant effect on the polymer structure, where
contents of the 1,2-polymerization unit in polymers were
determined to be 5% and 13% for 1d/Na2S2O3 and 1e/
Na2S2O3, respectively. The broader Mw/Mn and the smaller
Mn of the polymer prepared in the absence of Na2S2O3 might
be due to the chain transfer reaction. One possible explana-
tion can be made by the fact that iodine is known to add to
the double bond of allene moieties to yield allyl iodide
derivatives, which may bring out the chain transfer reactions.
In practice, the molecular weight of the polymer became much
smaller (Mn ) 5820, Mw/Mn ) 1.30) by 1f in the presence of
allyl iodide. See, for example: Friesen, R. W.; Bayly, C. I.;
Fogg, J. A. J. Org. Chem. 1995, 60, 448. and references
therein.
(21) In ref 10a, the polymerization of 1,2-butadiene by [(π-allyl)-
NiX]2 (X ) Cl, Br, and I, without PPh3) were reported, where
the ratio of the unsubstituted olefinic unit in the resulting
polymer increased in the same order.
(22) In ref 10a, the polymerization rate of 1,2-butadiene was also
studied by [(π-allyl)NiX]2 (X ) Cl, Br, and I) in the absence
of any ligands, where the rate is reported to increase in the
order Cl < Br < I.
(23) By comparing the kinetic coefficients of allylnickel carboxyl-
ates (1a-1c) with those of allylnickel halides (1d-1f), the
higher polymerization activity of 1d-1f than 1a-1c can be
observed, from which one might expect a higher content of
1,2-polymerization unit in the polymers by 1d-1f. However,
1d-1f provided polymers with lower 1,2-polymerization
contents, which might be ascribed to the difference in the
steric factor of the ligands.
(24) Hoff, S.; Brandsma, R. S.; Arena, J. K. Trav. Chim. Pay-Bas.
1968, 87, 916.
(25) Becconsall, J. K.; Job, B. E.; O’Brien, S. J. Chem. Soc., Part
A 1967, 423.
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