Polymerization of 1-Phosphaisoprene: Synthesis and Characterization of a Chemically Functional Phosphorus Version of Natural Rubber

Article abstract of DOI:10.1002/anie.201703590

Macromolecules derived from 1,3-dienes, such as polyisoprene (or natural rubber), are of considerable importance in polymer science. Given the parallels between P=C and C=C bonds, the prospect of polymerizing P-containing 1,3-dienes, such as 1-phosphaisoprene, is intriguing due to the unique chemical functionality imparted by the heavier element combined with their structural relationship to natural rubber. Herein, we report the synthesis, characterization and coordination chemistry of the first polymers derived from Mes*P=CR?CH=CH₂ (Mes=2,4,6-t-Bu₃C₆H₂; R=H, Me). In the case of 1-phosphaisoprene (R=Me), the monomer is isolable and its anionic polymerization affords a polymer that retains P=C bonds in its microstructure. The chemical functionality of these novel materials is demonstrated by forming the macromolecular gold(I) complex where the P=C bond is retained for further chemical elaboration.

Full text of DOI:10.1002/anie.201703590

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Accepted Article
Title: Polymerization of 1-phospha-isoprene: Synthesis and
Characterization of a Chemically Functional P-Version of Natural
Rubber
Authors: Klaus Dück, Benjamin W. Rawe, Michael R. Scott, and Derek
P. Gates
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201703590
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10.1002/anie.201703590
Angewandte Chemie International Edition
COMMUNICATION
Polymerization of 1-Phospha-isoprene: Synthesis and
Characterization of a Chemically Functional P-Version of Natural
Rubber
Klaus Dück, Benjamin W. Rawe, Michael R. Scott and Derek P. Gates*
Dedication ((optional))
Abstract: Macromolecules derived from 1,3-dienes, such as
polyisoprene (or natural rubber), are of considerable importance in
polymer science. Given the parallels between P=C and C=C bonds,
the prospect of polymerizing P-containing 1,3-dienes, such as 1-
phospha-isoprene, is intriguing due to the unique chemical
functionality imparted by the heavier element combined with their
structural relationship to natural rubber. Herein, we report the
synthesis, characterization and coordination chemistry of the first
fascinating macromolecules that possess two types of
functionality: a unit of unsaturation and a P-moiety. Herein, we
report the synthesis and characterization of the first examples of
poly(1-phospha-1,3-butadiene) and poly(1-phospha-isoprene),
P-versions of natural rubber.
As a potential monomer for polymerization studies, the
known P-Mes*-substituted 1-phospha-1,3-butadiene (Mes* =
2,4,6-tri-tert-butylphenyl) caught our attention.[14] Interestingly,
the authors referred to the “instability of 1-phospha-1,3-
butadiene which tends to polymerize.” No details of the
postulated “polymers” were provided. Using a hybrid of the
procedures reported for 1-phospha-1,3-butadiene and 1-
phospha-isoprene,[14, 15] a THF solution of bromophosphaalkene
1 was treated with vinylmagnesium bromide in the presence of
[Pd(PPh3)4] (Scheme 1). After 24 h, methanol was added and
the crude product was isolated as a viscous brown oil. Analysis
of a CDCl3 solution of the crude product by 31P{1H} NMR
spectroscopy did not show a sharp signal that could be assigned
to the 1-phospha-1,3-butadiene monomer (δ = 271 ppm).[14] Only
broad signals were observed which, combined with the viscous
nature of the solution, were suggestive of a polymer. Following
additional purification and precipitation steps, the polymeric
product, 2, was isolated as a yellow glass. Importantly, analysis
of this isolated material by GPC-MALS (Figure S4 in SI)
confirmed the polymeric nature of 2 (Mn = 6,000 g mol-1;
ÐM = 1.07). It is plausible that the narrow polydispersity is a
consequence of fractionation of the polymer during the extensive
work-up and/or an anionic polymerization mechanism initiated
by excess vinylmagnesium bromide.
polymers derived from Mes*P=CR–CH=CH2 (Mes*
= 2,4,6-t-
Bu3C6H2; R = H, Me). In the case of 1-phospha-isoprene (R = Me),
the monomer is isolable and its anionic polymerization affords a
polymer that retains P=C bonds in its microstructure. The chemical
functionality of these novel materials is demonstrated by forming the
macromolecular-gold(I)-complex where the P=C bond is retained for
further chemical elaboration.
Goodyear’s 1839 discovery of the vulcanization of natural rubber,
obtained from the hevea brasiliensis tree, represents a landmark
of human history and is the foundation of the modern rubber
industry.[1] Subsequently, the homo- and co-polymerization of
isoprene (or related dienes) with olefins such as isobutylene or
styrene led to synthetic rubbers. A common feature of polymers
from di-olefins is that they retain a C=C functionality that may be
further elaborated by crosslinking or related addition reactions.
The
macromolecules is a rapidly growing area that provides access
to materials with unique physical and chemical properties.[2, 3]
introduction
of
main
group
elements
into
A
principal limitation to the widespread development of this field is
the lack of general methods to connect inorganic elements into
long chains. Given the close analogy between P=C and C=C
bonds,[4] we have sought to extend the general method of olefin
polymerization to the P=C bonds of phosphaalkenes.[5-7] In
particular, the homo- and co-polymerization of the mono-
phosphaalkene MesP=CPh2 has led to functional materials that
are useful as catalyst supports, as templates for self-assemblies,
and as potential luminescent sensors.[8] We now turn our
attention to the potential use of rare molecules with both P=C
and C=C bonds[9-13] as monomers for polymerization studies.
Mes*
P
H
C
C
H
H
H2C
P
+ 3 (C2H3)MgBr
H
H
H
H
C
H
C
C
P
C
C
H
P
C
Mes*
Br
C
H
[Pd(PPh3)4]
(10 mol%)
Mes*
x
Mes*H
y
z
n
1
2
Scheme 1. Procedure used to prepare poly(1-phospha-1,3-butadiene) 2 (Mes*
= 2,4,6-tri-tert-butylphenyl). The spectroscopic data collected for 2 suggests
that x >> y, z.
We hypothesized that the polymerization of P-analogues of
1,3-butadiene and isoprene may provide an avenue to
There are three possible polymer microstructures for poly(1-
phospha-1,3-butadiene) 2 (x, y and z) in addition to several
stereoisomers. Thus, multinuclear NMR spectra were recorded
in a preliminary effort to elucidate the microstructure of this novel
macromolecule. The 31P{1H} NMR spectrum of 2 in CDCl3 is
shown in Figure 1(i). Particularly striking is that the predominant
signals are the broad downfield resonances at 256 and 246 ppm,
assigned to phosphaalkene isomers. It can therefore be
concluded that the polymerization of the putative 1-phospha-1,3-
[*]
Dr. K. Dück, B. W. Rawe, M. R. Scott, Prof. Dr. D. P. Gates
Department of Chemistry
University of British Columbia
2036 Main Mall, Vancouver, BC, V6T 1Z1 (Canada)
E-mail: dgates@chem.ubc.ca
Supporting information for this article is given via a link at the end
of the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201703590
Angewandte Chemie International Edition
COMMUNICATION
butadiene monomer occurs mainly through the C=C bond (i.e.
microstructure x in 2). Polymer 2 is a rare example of a
macromolecule featuring P=C double bonds, and opens the door
to a broad spectrum of chemical functionalization possibilities. In
addition to the aforementioned phosphaalkene signals,
resonances were observed at 22, –6, –69 and –82 ppm that are
tentatively ascribed to phosphine moieties (i.e. y and/or z in 2).
One or more of these signals may also reflect small degrees of
oxidation that may have occurred during aerobic workup.
Although an appropriate model compound is not known, we note
that the 31P NMR shifts of PhPMe(CH=CH2) and
MesP(CH2CH=CH2)2 are –31.3 and –33.2 ppm, respectively,[16,
the isolable 1-phospha-isoprene monomer 4 which is readily
accessed from phosphaalkene 3 following a cross coupling
procedure (Scheme 2).[15] The reaction is near quantitative as
inferred by 31P{1H} NMR spectroscopy (δ = 263.8 ppm for 4,
Figure S5) provided that the product is worked-up within ca. 15
min after mixing (yield = 78%). Longer reaction periods (ca. 24
h) afforded mixtures of poly(1-phospha-isoprene) 5 along with
monomer 4 and Mes*P=CHMe (δ = 250 ppm, Figure S6).[19]
Presumably, polymerization was initiated by the excess Grignard
reagent. Following precipitation of a CH2Cl2 solution of the crude
polymer with MeOH (×3), pure poly(1-phospha-isoprene) 5 (trial
1) was isolated as an off-white powder (yield
= 38%).
17]
whereas the vinyl polymer, [PhP-CMe=CMe]n, shows signals
Remarkably, the 31P{1H} NMR spectrum of 5 (trial 1) in CDCl3
solution (Figure 1(ii)) reveals broad signals at 235 and 225 ppm
consistent with the predominance of microstructure x for 5 (trial
1). The presence of smaller resonances at –48 and –52 ppm
have not been assigned unequivocally, although we presume
that they may be attributed to microstructures y and/or z of 5.
at –5 and –9 ppm.[18]
1
The H NMR spectrum (Figure S2 in SI) of poly(1-phospha-
1,3-butadiene) 2 reveals signals at 1.47, 1.35 and between 7.7 –
7.3 ppm characteristic of the Mes* moiety. In addition, a signal
detected at 7.27 ppm was assigned to the P=CH moiety (cf.
Mes*P=CHMe: δ = 7.25).[19] The backbone –CH-CH2– moieties
of microstructure x in 2 are detected as broad signals at 2.15
and 2.91 ppm and are correlated by HSQC to a broad
resonance in the 13C{1H} NMR spectrum (δ = 40.1 ppm). The
13C{1H} NMR spectrum (Figure S3 in SI) also clearly shows a
broad signal assigned to the P=C moiety (δ = 182.6 ppm).
Although conclusive evidence for microstructures y and/or z
could not be obtained, it should be noted that broad signals are
observed in the 1H NMR spectrum at 4.95 and 5.65 ppm,
perhaps attributable to vinylene moieties (cf. Ph2PCH=CHMe: δ
= 6.4 – 6.1 ppm).[20] These signals correlated by HSQC to
13C{1H} signals at 119.6 and 130.5 ppm, respectively.
H
C
H
H
C
C
P
Mes*
Me
4
[Init.] = n-BuLi
trial 2: 10 mol%
trial 3: 5 mol%
Me
Br
+ 3 (C2H3)MgBr
P
C
[Pd(PPh3)4]
(10 mol%)
Mes*
Mes*
P
3
Me
C
C
H
H
C
H
H2C
P
Me
H
H
C
H
C
C
P
C
trial 1
C
Mes*
x
H
Mes*Me
y
z
n
5
Scheme 2. Procedures used to prepare poly(1-phospha-isoprene) 5.
The anion-initiated polymerization of monomer 4 in THF was
examined by treating it with n-BuLi at 50 °C (trial 2: 10 mol%;
trial 3: 5 mol%, Scheme 2). Each trial was repeated twice with
monomer 4 of similar purity and similar results were obtained.
Upon addition of the initiator the yellow solution of monomer
immediately turned purple. The reaction was monitored by
31P{1H} NMR spectroscopy until the signals assigned to
monomer 4 were completely replaced by those assigned to
polymer 5 (ca. 3 d). At this time, MeOH was added to precipitate
poly(1-phospha-isoprene) 5 which was further purified by two
additional precipitations with MeOH (trial 2: yield = 39%; trial 3:
yield = 37%). The 31P{1H} NMR spectra of 5 are shown in Figure
1(iii) and (iv) for trials 2 and 3, respectively. Expectedly, the
features are quite similar to those for the one-pot polymerization
of 4 [Figure 1(ii)].
Figure 1. 31P{1H} NMR spectra (CDCl3, 121 MHz) of: (i) poly(1-phospha-1,3-
butadiene) 2, (ii) poly(1-phospha-isoprene) 5 (trial 1) from one-pot synthesis,
(iii) poly(1-phospha-isoprene) 5 (trial 2) isolated from the polymerization of 4
with n-BuLi (10 mol%), (iv) poly(1-phospha-isoprene) 5 (trial 3) isolated from
the polymerization of 4 with n-BuLi (5 mol%), (v) isolated product after treating
poly(1-phospha-isoprene) 5 (trial 1) with tht·AuCl (1 equiv per P).
Each polymer received additional characterization by 1H
(Figure S7) and 13C{1H} NMR spectroscopy (Figure S8) along
with HSQC and HMBC experiments. Representative spectra are
shown in the supporting information and were virtually identical
in each case. The signals assigned to the Mes* moiety
dominated. Importantly, the 1H NMR spectrum shows a broad
shoulder on the resonances assigned to t-Bu that can be
correlated by HSQC to broad signals in the 13C{1H} NMR
spectrum at 19.7, 44.6 and 46.7 ppm assigned to P=CCH3 and
the backbone –CH-CH2– moieties, respectively. In addition, the
Although satisfied with the successful isolation and
characterization of the first poly(1-phospha-1,3-butadiene), it
was not possible to confirm that 1-phospha-1,3-butadiene was
present as an intermediate. Therefore, we turned our attention to
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COMMUNICATION
13C{1H} NMR spectrum shows
a
broad downfield signal
dry solid was a brittle glass. Examination of the solid by wide-
angle X-ray scattering (WAXS) showed only broad scattering
(Figure S14), consistent with a primarily amorphous material.
Polymer 5 was also analyzed by differential scanning calorimetry
(DSC) to reveal a broad glass transition [Figure S15: Tg (onset)
= 95 °C, Tg (midpoint) = 110 °C]. Not surprisingly, this P-version
of natural rubber has a much higher Tg than natural rubber itself,
which is likely mostly due to the presence of the structurally rigid
Mes* group in the former.
attributable to the P=C bond (δ = 187.3 ppm). Although signals
in the region expected for vinylic protons were not observed in
either the 1H or 13C{1H} NMR spectra, the presence of
microstructures y and z for 5 cannot be ruled out. Clearly, it can
be concluded that microstructure x for 5 predominates for this 1-
phospha-isoprene polymer.
In an effort to rationalize these observations on the
microstructure of these new polymers, preliminary DFT
calculations were performed on monomer 4 and the possible
intermediates in its anionic polymerization (Figure S19) These
results suggest that the lowest energy intermediate arises when
Me– adds to the =CH2 moiety which could lead to
microstructures x or y in 5. The nearest energy intermediate
occurs with addition of Me– to the carbon of the P=C bond (ΔE =
+13.6 kcal/mol) which could lead to microstructure z in 5. We
note that addition of Me– at the P=C bond of 1-phospha-1,3-
butadiene, Mes*P=CH-CH=CH2, gives a slightly lower energy
intermediate with respect to addition to the =CH2 moiety. This
may, in part, rationalize the more complex microstructure
observed for polymer 2 when compared to 5.
Of particular interest are the molecular weights of these
novel P-versions of natural rubber. According to GPC-MALS
analysis (Figure S9−S11), the one-pot synthesized polymer (5
trial 1) was of modest molecular weight with narrow
polydispersity (Mn = 8,600 g mol-1; ÐM = 1.12). The anion-
initiated polymer 5 (trial 2: Mn = 2,400 g mol-1; ÐM = 1.05)
displayed a lower molecular weight than predicted for a 10:1
monomer to initiator ratio (ca. 3,300 g mol-1). With a 20:1
monomer to initiator ratio, the molecular weight approximately
doubled (trial 3: Mn = 4,200 g mol-1; ÐM = 1.10) but was still less
than predicted (ca. 6,600 g mol-1). Nonetheless, the data does
suggest that a living polymerization may be possible if extremely
high purity monomer is employed. It is noteworthy that in one
instance a very high molecular weight for 5 (Figure S12, Mn =
120,000 g mol-1, ÐM = 1.28) was obtained when a rather impure
monomer was treated with n-BuLi (5 mol%). Presumably, the
monomer impurities partially quenched the initiator resulting in a
much higher [M]:[I] ratio than intended and/or inducing partial
crosslinking. Regardless, this result demonstrates the exciting
prospect of using this methodology to obtain very high molecular
weight polymers.
Figure 2. MALDI-TOF mass spectrum of 5 (DCTB matrix and AgTFA) showing
tentative assignments.
To demonstrate the chemical functionality of 1-phospha-
isoprene polymer 5 with predominantly x microstructure, efforts
were made to coordinate the phosphaalkene moiety to gold(I).
Thus, 5 (trial 1, Mn = 8,600 g mol-1, ÐM = 1.12) was treated with
tht·AuCl (1 equiv per P atom) in CH2Cl2 solution and the
resultant polymer was precipitated and isolated as a colorless
powder. The 31P{1H} NMR spectrum of a solution of the isolated
product in CDCl3 is shown in Figure 1(v). It shows that the
product, assigned as 5·AuCl (δ = 186 ppm), displayed a
significantly upfield chemical shift compared to uncomplexed 5
yet is consistent with retention of the P=C bond. For comparison,
related P-Mes* phosphaalkene-gold(I) complexes show signals
at around 200 ppm.[21] Additional characterization of 5·AuCl was
obtained by using 1H and 13C{1H} NMR spectroscopy (Figure
S16−S17) and GPC-MALS (Figure S18), each consistent with
The one-pot synthesized polymer 5 (trial 1, GPC: Mn = 8,600
g mol-1) was further analyzed by MALDI-TOF MS (Figure 2) and
ions were detected that are consistent with the proposed
composition of 5. Notably, a regular pattern of ions was
observed that are spaced by the mass of the monomer unit (330
Da). Even though there appears to be significant fragmentation
and signal overlap which adversely affected the resolution of the
spectrum, signals can tentatively be assigned to [5n+Ag]+ with
chain lengths between n = 6 and 29. A preliminary investigation
of the physical properties of polymer 5 was conducted. Analysis
by thermogravimetric analysis (TGA) revealed that the polymer
was stable to weight loss until 272 °C (Tonset) where, in a single
sharp step, a weight loss was observed to give a ceramic yield
of 3.3 wt% (Figure S13). Although 5 when “wet” with solvent
exhibited rubbery properties (see Table of Contents graphic), the
the assignment as
a
metal-containing macromolecule.
Noteworthy, is the significant increase of the molecular weight
(Mn = 23,300 g mol–1, ÐM = 1.06) which is expected when
binding to the heavy gold(I) moiety.
Cl
Au
Mes*
P
Me
Mes*
P
Me
C
C
H
H
C
C
H
H
tht·AuCl
C
H
C
H
CH2Cl2
5·AuCl
5
Scheme 3. Synthesis of gold(I)-containing macromolecule 5·AuCl by treating
5 with tht·AuCl. For clarity just the predominant microstructure x is shown.
In closing, we have successfully prepared and characterized
the first polymers of 1-phospha-1,3-butadiene and 1-phospha-
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10.1002/anie.201703590
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COMMUNICATION
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These functional P-containing materials are rare examples of
polymers containing phosphaalkene moieties[22] and offer many
prospects for further derivatization and crosslinking of this
functional moiety. We have confirmed that poly(1-phospha-
isoprene) may be employed as a macromolecular ligand for
gold(I) which is of future interest in catalysis and nanochemistry,
amongst other possible uses. Furthermore, the successful
polymerization of P=C/C=C hybrid monomers opens the door to
explore radical or living anionic methods of polymerization to
afford random or block copolymers with unique architectures,
properties and functionality.
[4]
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The Carbon Copy, Wiley, New York, 1998; b) F. Mathey, Angew. Chem.
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[5]
[6]
Acknowledgements
This work was supported by the Natural Sciences and
Engineering Research Council (NSERC) of Canada. K.D. is
grateful to the Deutsche Forschungsgemeinschaft (DFG) for a
research fellowship. We are also grateful to Dr. Yun Ling of the
UBC-Mass Spectrometry & Microanalysis Facility for assistance
in obtaining and interpreting the MALDI-TOF spectra.
[7]
[8]
Keywords: gold
• inorganic polymer • phosphaalkene •
phosphorus • polymerization
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10.1002/anie.201703590
Angewandte Chemie International Edition
COMMUNICATION
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COMMUNICATION
Un-natural rubber. We report a P-
containing structural analogue of
polyisoprene. Namely, 1-phospha-
isoprene is polymerized with anionic
initiators to afford the first example of
a P-polymer of isoprene, the monomer
in natural rubber. The chemical
Klaus Dück, Benjamin W. Rawe,
Michael R. Scott, Derek P. Gates*
Page No. – Page No.
Polymerization of 1-Phospha-
isoprene: Synthesis and
Characterization of a Chemically
Functional P-Version of Natural
Rubber
functionality
of
poly(1-phospha-
isoprene) is demonstrated by its
binding of gold(I) to give novel metal-
containing macromolecules.
This article is protected by copyright. All rights reserved.