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Formation, structure and bonding of metalloid Al and Ga clusters. A challenge for chemical efforts
in nanosciences
Hansgeorg Schnckel, Dalton Trans., 2008 DOI: 10.1039/b718784j
Polymeric materials based on main group elements: the recent development of ambient
temperature and controlled routes to polyphosphazenes
Vivienne Blackstone, Alejandro Presa Soto and Ian Manners, Dalton Trans., 2008
DOI: 10.1039/b719361k
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PERSPECTIVE www.rsc.org/dalton | Dalton Transactions
This Perspective discusses the development of new routes to polyphosphazenes, [R2 P=N]n , that occur at
Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
ambient temperature and, in some cases, allow molecular weight control and access to narrow
molecular weight distributions and block copolymers. For example, the room temperature
silyl-carborane initiated ring-opening polymerisation of (NPCl2 )3 is described together with chain
growth condensation polymerisations of phosphoranimines Cl3 P=NSiMe3 and BrMePhP=NSiMe3 .
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Vivienne Blackstone graduated from the University of Bristol in 2005 with an MSci in Chemistry. She joined Prof. Ian Manners group in
2006, focusing her research on the polymerisation chemistry of phosphoranimines.
Alejandro Presa graduated from the University of Oviedo in 2000 with an MSc in Chemistry. He completed his Ph.D. in the group of Prof.
G. A. Carriedo and Prof. F. J. Alonso. He joined Prof. Ian Manners group in 2006 as a Postdoctoral Research Fellow, his scientic interests
involve block copolymers containing main group elements.
Ian Manners received his Ph.D. from the University of Bristol in 1985 in the area of transition metal chemistry (with N. G. Connelly). After
postdoctoral work in Germany (P. Paetzold), and in the USA (H. R. Allcock) he joined the University of Toronto, Canada in 1990. In 2005
he returned to Bristol to take up a Chair in Inorganic, Macromolecular and Materials Chemistry, supported by the award of a Marie Curie
Chair from the European Union and a Wolfson Research Merit Award from the Royal Society.
This journal is The Royal Society of Chemistry 2008 Dalton Trans., 2008, 43634371 | 4363
place and this translates into useful mechanical properties that
allow, for example, the formation of exible, free-standing lms.
To be of optimum interest, the synthesis of the monomer should
be convenient and scalable and the polymerisation should proceed
under mild and convenient conditions. In addition, the ability to
control molecular weight is highly desirable.16 In many cases the
current polymerisation approaches to inorganic polymer systems
are less than ideal and the discovery of new synthetic routes can
enhance opportunities for widespread development. In addition,
detailed studies of the mechanism of existing polymerisations that
occur at elevated temperatures offer potential improvements in
Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
4364 | Dalton Trans., 2008, 43634371 This journal is The Royal Society of Chemistry 2008
chemistry.50,51 Within the class of phosphoranimines, the N-
silylphosphoranimines, R3 P=NSiR3 , are of substantial interest as
they are employed as monomeric precursors to polyphosphazenes
by thermal,17,26,52,53 uoride ion-catalysed18,54 and living cationic
chain-growth condensation polymerisation.27,5559
In 1995, in collaboration with Allcock and coworkers, we
reported the rst ambient temperature synthesis of 1 via
the living cationic chain-growth polymerisation of trichloro-
(trimethylsilyl)phosphoranimine, Cl3 P=NSiMe3 (10), initiated by
trace amounts of PCl5 (Scheme 4).27,55,60 The bulk polymerisation
of 10 with trace amounts of PCl5 resulted in a two phase mixture,
Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
of which both phases were clear and colourless (Fig. 1). 1 H NMR
identied the top, more uid layer to be Me3 SiCl while 31 P{1 H}
NMR of the lower, more viscous layer showed a single resonance
from the reactions involving 2 and the strong Lewis acids. The at d 17.4 ppm characteristic of poly(dichlorophosphazene).
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Scheme 3
In order to determine the molecular weight of the polymers Fig. 1 Two phase mixture of Me3 SiCl (top layer) and [Cl2 P=N]n (bottom
layer) from the PCl5 -initiated bulk polymerisation of Cl3 P=NSiMe3 .
obtained from the ambient temperature ROP reaction of 2 initiated
by 8, the hydrolytically-stable polymer [(CF3 CH2 O)2 P=N]n was
prepared by halogen replacement reactions on 1 prepared from Gel permeation chromatography (GPC) of the air- and
the treatment of a 1 M 1,2-dichlorobenzene solution of 2 with moisture-stable polymer [(CF3 CH2 O)2 P=N]n , prepared by halo-
10 mol% of 8 (Scheme 3). Poly{bis(triuoroethoxy)phosphazene} gen replacement on 1 (Scheme 4), showed the polymer to have a
was prepared with 84% yield (M w = 1.12 105 g mol1 , PDI = high molecular weight (M n = 1.2 105 ) and a PDI of 1.8 versus
1.83). We are currently, collaboratively, further developing this new polystyrene standards. When a lower monomer to PCl5 ratio was
ambient temperature route to 1 and are attempting to elucidate used in an attempt to obtain lower molecular weight polymer
the ROP mechanism. GPC analysis showed a multimodal trace, indicating that the
heterogeneous nature of the system results in a lack of molecular
Living cationic chain-growth polymerisation of Cl3 P=NSiMe3 weight control in the bulk phase.
However, the same reaction in dichloromethane resulted in
Phosphoranimines with the general formula R3 P=NR have been quantitative conversions of the monomer 10 to 1 with narrow
the subject of many detailed studies over the past 60 years.4144 The molecular weight distributions. It was found to be possible to
rst examples were prepared by Staudinger and Mayer in 1919 control the molecular weight of the polymer by varying the
using tertiary phosphines and organic azides.45 Since the 1950s monomer to initiator ratio, an increase in the ratio of 10 to
the chemistry of phosphoranimines has attracted considerable PCl5 resulted in an increase in molecular weight (Table 1). This
attention due to their applications as aza-Wittig reagents,46,47 is characteristic of a living polymerisation without chain transfer
and ligands in main-group48,49 and transition-metal coordination and chain termination steps.
This journal is The Royal Society of Chemistry 2008 Dalton Trans., 2008, 43634371 | 4365
Table 1 Monomer : initiator ratio and molecular weight data for the conversion, one of the characteristics of a living polymerisation
polymerisation of 10 initiated by PCl5 (Fig. 2). The living nature of the cationic polymerisation of 10
was also demonstrated when the polymerisation of a 93 : 1 10 : PCl5
(Monomer : initiator)/
Phase mol mol1 Mwa Polydispersity index reaction was monitored by 31 P{1 H} NMR and 1 H spectroscopy.
It showed a linear relationship when ln([M]/[M]0 ) was plotted
Bulk 108 210 000 1.8 against time, indicating rst-order kinetics, another characteristic
Bulk 15.5 41 000 b
of a living polymerisation (Fig. 3).
Solution 5.4 7 000 1.20
Solution 10.8 11 000 1.04
Solution 22.6 14 000 1.04
a
Using GPC with 0.1% n Bu4 NBr (w/w) in THF eluent. b Multimodal GPC
trace.
Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
Scheme 5
4366 | Dalton Trans., 2008, 43634371 This journal is The Royal Society of Chemistry 2008
as side-group steric bulk and the presence of electron-donating
substituents. As for the polymerisation of 10, the polymer formed
in the reaction of XRR P=NSiMe3 with PCl5 remains active after
all monomer has been consumed, this activity has been used for
the synthesis of block copolymers.61,63
Scheme 6
This journal is The Royal Society of Chemistry 2008 Dalton Trans., 2008, 43634371 | 4367
Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
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Scheme 9
4368 | Dalton Trans., 2008, 43634371 This journal is The Royal Society of Chemistry 2008
Scheme 12 Scheme 14
This journal is The Royal Society of Chemistry 2008 Dalton Trans., 2008, 43634371 | 4369
Table 2 Molecular weight data for polymer 24
Scheme 17
was obtained in all the cases (Table 2). The mechanism of this
+
Fig. 7 Molecular structure of [19] with thermal ellipsoids at the 30% polymerisation is now under investigation in our laboratory.
probability level. Hydrogen atoms and the bromide counteranion are
omitted for clarity (reprinted with permission from ref. 29. Copyright Summary
2006 American Chemical Society).
From considerations of polymerisation mechanisms and the prob-
able reactive intermediates involved, new routes to polyphosp-
hazenes have been developed that operate under mild temperatures
and that permit, in some cases, molecular weight control and
access to controlled polymer architectures. Interesting mechanistic
questions remain and further understanding and optimisation of
the polymerisations are desirable. The routes offer new opportu-
Scheme 16
nities for the synthesis of polyphosphazene homopolymers and
we treated the phosphoranimine 18 with (Me3 O)P. Surprisingly, block copolymers and should provide additional momentum to
the analysis by 31 P{1 H}NMR after 4 h in CH2 Cl2 at room the further development this interesting eld.
temperature showed the quantitative formation of the known
polyphosphazene [Me2 P=N]n (21) (d = 7 ppm) instead of the Acknowledgements
salt [(Me3 O)PPMe2 =NSiMe3 ]Br (22). The polyphosphazene was
isolated in good yield as a brous solid by precipitation into We thank our collaborators on relevent parts of the work
pentane (for an example of a solvent cast lm see Fig. 8). Mea- described in this article namely, Christopher A. Reed (University
surements by dynamic light scattering showed that the molecular of California at Riverside) and Harry R. Allcock (Penn State
weight was high (Rh = 6.8 nm). We also explored the generality of University). V.B. thanks the States of Jersey for a Postgraduate
the reaction using different substituted bromophosphoranimines Scholarship. A.P. thanks the European Union for a Marie Curie
(Scheme 17).29 Fellowship. I.M. thanks the European Union for a Marie Curie
Chair and the Royal Society for a Wolfson Research Merit Award.
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