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This paper is published as part of a Dalton Transactions theme issue:

Dalton Discussion 11: The Renaissance of Main Group

Chemistry
Guest Editor: John Arnold
University of California, Berkeley, CA, USA
23 - 25 June 2008

Published in issue 33, 2008, of Dalton Transactions

Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
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Image reproduced with permission of Manfred Scheer

Papers published in this issue include:

The coordination chemistry of group 15 element ligand complexesa developing area

Manfred Scheer, Dalton Trans., 2008 DOI: 10.1039/b718179p

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

Recent developments in the chemistry of low valent Group 14 hydrides

Eric Rivard and Philip P. Power, Dalton Trans., 2008 DOI: 10.1039/b801400k

Chemistry and physics of silicon nanowire

Peidong Yang, Dalton Trans., 2008 DOI: 10.1039/b801440j

Visit the Dalton Transactions website for more cutting-edge inorganic and organometallic research
www.rsc.org/dalton
 PERSPECTIVE www.rsc.org/dalton | Dalton Transactions

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*
Received 19th December 2007, Accepted 11th February 2008
First published as an Advance Article on the web 23rd July 2008
DOI: 10.1039/b719361k

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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Recent works on donor-stabilised cationic phosphoranimines are also discussed.

1. Introduction teristics such as high oxygen permeability and hydrophobicity also

Polymers containing main group elements are of considerable in-
terest as they often possess unique characteristics or combinations
of properties that complement those normally available with the
extensively developed organic macromolecular materials.15 For
example, polysiloxanes [R2 SiO]n represent a major commercial
product worldwide because of the combination of low temperature
exibility and high thermoxidative stability that arise from the
main chain of alternating silicon and oxygen atoms. Other charac-
School of Chemistry, University of Bristol, Bristol, UK BS8 1TS. E-mail:
Ian.Manners@bris.ac.uk.; Fax: +44 (0)117 929 0509; Tel: +44 (0)117 928
7650
Based on the presentation given at Dalton Discussion No. 11, 2325 June
2008, University of California, Berkeley, USA.
lead to major applications. On the other hand, polysilanes with
an all-silicon backbone exhibit remarkable electronic properties
as the r-electrons in the main chain are extensively delocalised
and possess semiconductive and photoconductive properties.
These materials also function as precursors to SiC ceramics and
irradiation with near UV light allows their use as photoresists
in microlithography. Recent advances in the area of main group
polymers have led to a variety of new polymer systems such as
polystannanes,6 polythionylphosphazenes,7 polyphosphaalkenes,8
polyphosphinoboranes, and a variety of other phosphorus-912 and
boron-containing materials.1315
To be generally useful as materials, polymers need to be of
substantial molecular weight (typically number average molecular
weights (M n ) over 10 000). This allows chain entanglement to take

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.

Alejandro Presa Soto, Vivienne Blackstone and Ian Manners

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
terms of the reaction conditions and control over the resulting
polymer architectures.
In this article we discuss some of our groups recent work on
polyphosphazenes [R2 P=N]n . These materials represent one of
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the most interesting and promising inorganic polymer systems.
Although developed commercially using a high temperature
ring-opening polymerisation (ROP) route, a variety of other
condensation methods were developed in the 19801992 period.
These also involved relatively high temperatures (>100 C).1720
Here we discuss some of our groups work along with, in several
cases, projects that involve collaborators, on the development
of new routes to polyphosphazenes that occur at ambient tem-
perature and, in some cases, allow molecular weight control
and access to narrow molecular weight distributions and block
copolymers.
2. Synthesis of poly(dichlorophosphazene)
Poly(dichlorophosphazene), [Cl2 P=N]n (1) plays a key role in
phosphazene polymer chemistry by providing access to polyphos-
phazenes with an extensive range of physical and chemical proper-
ties via halogen substitution with O- and N-based nucleophiles.21
Polymer 1 was rst prepared by Stokes in 1897,22 however
it was not until the mid-1960s that Allcock and co-workers
synthesised the rst examples of soluble, uncrosslinked high
molecular weight polyphosphazenes via the thermal (ca. 250 C)
ROP of [N3 P3 Cl6 ] (2) (Scheme 1) followed by halogen side group
replacement.2325 Since then a number of synthetic routes to
polyphosphazenes have been developed, however these require
elevated temperatures, provide no molecular weight control and
produce polymer with broad molecular weight distributions.1719,26
Over the past 12 years our group, in some cases in collab-
oration with others, has developed three ambient temperature
syntheses, two to poly(dichlorophosphazene) 127,28 and one to
poly(organophosphazenes) with side groups attached by direct
PC bonds.29
Scheme 1
4364 | Dalton Trans., 2008, 43634371
Scheme 2
Ambient temperature ROP of [N3 P3 Cl6 ] catalysed by silylium ions
As noted above, the most commonly used synthetic route to
1 is the thermal (ca. 250 C) ROP of the cyclic phosphazene
trimer 2 (Scheme 1).23,25 This versatile route provides access to
many derivatives of high molecular weight polyphosphazenes via
macromolecular substitution reactions on 1 with O- and N-based
nucleophiles such as alkoxides, aryloxides and amines, however it
has also many disadvantages. These include the elevated tempera-
ture required to cause ROP, lack of molecular weight control and
the high polydispersity indexes (PDIs) of polymer prepared via this
method.30 Also, in the melt, the reaction must be terminated before
70% conversion to prevent cross-linking reactions occurring and
isolated yields of soluble polymer are often <40%.21
Studies have shown that ROP can be catalysed by certain Lewis
acids, such as BCl3 31 or AlCl3 ,32 allowing the process temperature
to be reduced to ca. 200 C. Magill and co-workers were able
to reduce the reaction time to 1 h at 210 C by using a 1,2,4-
trichlorobenzene solution of 2 with sulfamic acid as a catalyst
in the presence of the promoter, calcium sulfate dihydrate.30
Following this, Carriedo and co-workers reported a one-pot
synthesis of 1 directly from PCl5 and NH4 Cl, using the same
reaction conditions at 210 C and high molecular weight polymer
was obtained within 3.5 h.33
Although the mechanism of the ROP of 2 is still not clearly
understood the most commonly proposed pathway involves initial
thermally-induced or Lewis acid-assisted ionisation of a chloride
ion from phosphorus to form the cationic intermediate [N3 P3 Cl5 ]+
(3). This is followed by nucleophilic attack of 2 on 3 (Scheme 2).21
However, cationic derivatives of 2 are extremely rare and
coordinatively unsaturated cations of type 3 are unknown. Various
attempts have been made to abstract a chloride ion from 2 to
generate a cation of type 3. However, the low basicity of 2
(pK a = 6 in nitrobenzene)34 requires an extremely strong Lewis
or Brnsted acid for the abstraction of a chloride ion or to achieve
either protonation or coordination.3539
In 2006 Reed and co-workers reported protonated, methy-
lated and silylated derivatives of 2 by utilising extremely non-
coordinating carborane anions.40 They showed that phosphazene
nitrogen coordination, rather than chloride abstraction, resulted
This journal is The Royal Society of Chemistry 2008

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from the reactions involving 2 and the strong Lewis acids. The
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resulting cations (49) are potential precursors to 3 and may
provide an insight into the thermal ROP of 2. In collaboration
with Reed and coworkers, we recently reported the rst ambient
temperature ROP of 2 by employing the above trialkylsilyl
carboranes as initiators.28 We found that treatment of 2 [d (31 P) =
20 ppm]23,25 with 10 mol% of the N-silylated derivatives (69) or the
trialkylsilyl carborane precursor in 1,2-dichlorobenzene at 25 C
resulted in complete conversion to polydichlorophosphazene 1
[d (31 P) = 18 ppm]23,25 as determined by 31 P NMR spectroscopy
(Scheme 3). Of the four silyl derivatives 69 the most active catalyst
for the ROP of 2 was [Et3 Si(N3 P3 Cl6 )][HCB11 H5 Br6 ] (8). However,
we found that very low concentrations of 2 appeared to hinder
ROP. This is characteristic of cyclic monomers with a low degree
of ring strain and is consistent with the energetics of ROP recently
deduced for the cyclic thionylphosphazene [NSOCl(NPCl2 )2 ].7
Scheme 3
In order to determine the molecular weight of the polymers
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
the treatment of a 1 M 1,2-dichlorobenzene solution of 2 with
10 mol% of 8 (Scheme 3). Poly{bis(triuoroethoxy)phosphazene}
was prepared with 84% yield (M w = 1.12 105 g mol1 , PDI =
1.83). We are currently, collaboratively, further developing this new
ambient temperature route to 1 and are attempting to elucidate
the ROP mechanism.
Living cationic chain-growth polymerisation of Cl3 P=NSiMe3
Phosphoranimines with the general formula R3 P=NR have been
the subject of many detailed studies over the past 60 years.4144 The
rst examples were prepared by Staudinger and Mayer in 1919
using tertiary phosphines and organic azides.45 Since the 1950s
the chemistry of phosphoranimines has attracted considerable
attention due to their applications as aza-Wittig reagents,46,47
and ligands in main-group48,49 and transition-metal coordination
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,
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
at d 17.4 ppm characteristic of poly(dichlorophosphazene).
Scheme 4
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 .
Gel permeation chromatography (GPC) of the air- and
moisture-stable polymer [(CF3 CH2 O)2 P=N]n , prepared by halo-
gen replacement on 1 (Scheme 4), showed the polymer to have a
high molecular weight (M n = 1.2 105 ) and a PDI of 1.8 versus
polystyrene standards. When a lower monomer to PCl5 ratio was
used in an attempt to obtain lower molecular weight polymer
GPC analysis showed a multimodal trace, indicating that the
heterogeneous nature of the system results in a lack of molecular
weight control in the bulk phase.
However, the same reaction in dichloromethane resulted in
quantitative conversions of the monomer 10 to 1 with narrow
molecular weight distributions. It was found to be possible to
control the molecular weight of the polymer by varying the
monomer to initiator ratio, an increase in the ratio of 10 to
PCl5 resulted in an increase in molecular weight (Table 1). This
is characteristic of a living polymerisation without chain transfer
and chain termination steps.
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.
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The initiation step was shown to involve the reaction of one

molecule of monomer, 10, with two molecules of PCl5 to yield
the cationic initiating species [Cl3 P=N=PCl3 ]PCl6 ([11]PCl6 ). The
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initiating species was then proposed to react with further molecules

of monomer to yield 1 with elimination of Me3 SiCl as a byproduct
(Scheme 5).

Fig. 2 Molecular weight vs. percent conversion for a 46 : 1 10 : PCl5

reaction in CH2 Cl2 (reprinted with permission from ref. 55. Copyright
1996 American Chemical Society).

Scheme 5

Various initiators were studied for the cationic polymerisation of

10, such as Lewis acid main group and transition metal chlorides,
and a number of trityl cations.55 Phosphorus(V) species such as
PX5 (X = Cl, Br) and PhPCl4 rapidly initiated the polymerisation
of 10 at room temperature, as did other group 15 chlorides such
as SbCl5 . However, high oxidation state transition metal halides
such as TiCl4 , TaCl5 and WCl6 , and main group Lewis acids such
as AlCl3 , SnCl4 and POCl3 were not effective initiators.
The activity of the living chains was investigated by prepar-
ing a solution of poly(dichlorophosphazene) in CH2 Cl2 with a
monomer to PCl5 ratio of 9.3 : 1. A portion of the fully con-
verted polymer sample (as determined by 31 P{1 H} spectroscopy)
was removed and substituted with NaOCH2 CF3 to yield the
hydrolytically-stable polymer [(CF3 CH2 O)2 P=N]n with Mn =
1.1 104 and PDI = 1.09. Addition of further monomer to the
remaining poly(dichlorophosphazene) resulted in the conversion
of 10 to 1 over 24 h. GPC analysis of the OCH2 CF3 -substituted
Fig. 3 Kinetic study of a 93 : 1 10 : PCl5 reaction as monitored by 1 H
polymer showed the polymer to have a molecular weight M n = NMR (reprinted with permission from ref. 55. Copyright 1996 American
4.4 104 and PDI = 1.17. This showed that active chain ends can Chemical Society).
resume growth upon the addition of further monomer to the reac-
tion mixture. This characteristic of the cationic polymerisation has The ambient temperature polymerisation of mono- and
been used to prepare high molecular weight polyphosphazenes55 diorgano-substituted phosphoranimines, XRR P=NSiMe3 initi-
and phosphazene block copolymers.61,62 ated by PCl5 in both solution and bulk state have also been
By removing aliquots from a polymerisation of 10 initiated investigated.56 Both routes yielded poly(organophosphazenes)
by PCl5 (46 : 1 ratio) at regular intervals and substituting with with fairly controllable but moderate molecular weights and
NaOCH2 CF3 it was shown that the polymerisation is charac- relatively narrow polydispersities, however the polymerisations
terised by a linear increase in molecular weight versus percentage carried out in CH2 Cl2 appeared to be hindered by factors such

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

New, high yield synthesis of Cl3 P=NSiMe3 (10)

Scheme 7
Trichloro(trimethylsilyl)phosphoranimine, 10, the precursor for
the ambient temperature synthesis of poly(dichlorophosphazene)
was rst prepared by Niecke and Bitter from PCl5 and LiN(SiMe3 )2
in 1973.64 By reducing the reaction temperature from 10 to 78 C
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we improved the yield from 20 to 40%.65 However, the use of

PCl5 , an initiator for the cationic chain growth polymerisation,
as a starting material unavoidably resulted in signicant amounts
of oligomeric and polymeric byproducts. The chlorosilylamine,
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ClN(SiMe3 )2 , was also a common byproduct that could not

be separated from 10 by distillation and was found to inhibit
polymerisation. The synthesis of BrR2 P=NSiMe3 via halogena-
tion of phosphorus(III) precursors, R2 PN(SiMe3 )2 , using bromine
reported by WisianNeilson and Neilson26 led us to explore a
similar route for the synthesis of 10. We found that the strong
chlorinating agent, SO2 Cl2 , oxidised Cl2 PN(SiMe3 )2 eliminating
Me3 SiCl and SO2 as byproducts (Scheme 6). The procedure is
carried out within the mild temperature range of 0 C to room
temperature. The starting aminophosphine, Cl2 PN(SiMe3 )2 , is
made in situ from PCl3 and LiN(SiMe3 )2 thereby avoiding the
need for PCl5 and minimising losses in yield due to oligomeric
and polymeric byproducts. After distillation to remove Et2 O and
Me3 SiCl we were able to obtain yields of 80% with only trace
amounts of Me3 SiCl present.66
Fig. 4 Molecular structure of [Cl3 P=N(PCl2 =N)2 =PCl3 ]Cl with ther-
mal ellipsoids at the 50% probability level. The CH2 Cl2 molecule is
omitted for clarity (reprinted with permission from ref. 59. Copyright
2004 American Chemical Society).
We also prepared carbophosphazene macrocycles from the
reaction of the 5-membered chain [Cl3 P=NPCl2 =N=PCl3 ]Cl
with Me3 SiN=C=NSiMe3 (Scheme 8). 31 P{1 H} NMR re-
vealed the presence of two species, [NCCl(NPCl2 )3 ]2 and
[NCCl(NPCl2 )3 ] (ca. 1 : 1 ratio). The novel 16-membered macro-
cycle [NCCl(NPCl2 )3 ]2 was characterised by X-ray diffraction
representing the largest discrete carbophosphazene ring to be
characterised crystallographically.71 The more soluble product was
assigned as the eight-membered derivative [NCCl(NPCl2 )3 ].

Scheme 6

New, convenient synthesis of linear phosphazene salts

As a consequence of our investigations of the chemistry of 10 a new

route to the phosphazene salt [11]Cl, a precursor to halogenated,
polymerisable heterocycles, was developed by our group in 2004.59
Previous routes involved multistep procedures and often the use
of highly toxic and corrosive reagents.6769 We found that the
strong donor, 4-(dimethylamino)pyridine (DMAP) would remove
an equivalent of PCl5 from the hexachlorophosphate ion of the Scheme 8
initiating species, [11]PCl6 , for the cationic polymerisation of 10
to yield the target salt [11]Cl (Scheme 7). This one-pot synthesis
routinely gives pure product with yields exceeding 75%. 3. Donor-stabilised cationic phosphoranimines
Higher linear homologues were also prepared by reacting [11]Cl and a new ambient temperature route to
with 1, 2 and 3 equivalents of 10 to yield the phosphazene chains poly(alkyl/aryl)phosphazenes
[Cl3 P=N(PCl2 =N)x =PCl3 ]Cl (x = 1, 2 and 3, respectively) in
moderate yields. The ve- and seven-membered chains were crys- Cationic N-silylphosphoranimines, [R2 P=NSiR3 ]+ , are believed
tallographically characterised, both adopt a cistrans geometry to be involved as key intermediates in the thermal condensation
and have bond lengths and angles similar to those in 1 (see e.g. route to poly(alkyl/aryl)phosphazenes discovered by Neilson and
Fig. 4).70 Wisian-Neilson (Scheme 9).17 However, only a few examples

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Scheme 9
of such cationic species have been reported.7274 Motivated
by the potentially interesting reactivity of this species our
group has studied the synthesis and isolation of cationic N-
silylphosphoranimines and developed a new ambient temperature
route to poly(alkyl/aryl)phosphazenes.
Synthesis and characterisation of nitrogen-donor-stabilised
N-silylphosphoranimine cations
Initial attempts to generate N-silylphosphoranimine cations in-
volved the stoichiometric reaction of 10 with the halide abstractor
AgOTf (OTf = OSO2 CF3 ) in CH2 Cl2 at 25 C. However, in lieu of
obtaining the expected triate derivative (TfO)Cl2 P=NSiMe3 , we
observed the slow but quantitative formation of polydichlorophos-
phazene [Cl2 P=N]n and TfOSiMe3 after 18 h.75 When we repeated
the reaction of 10 with Ag[X] (X = OTf, BF4 and SbF6 ) in
the presence of the strong donor 4-(dimethylamino)-pyridine
(DMAP) a new product was isolated as colourless needles (mp =
98100 C) and characterised in solution and in the solid-state
(Fig. 5) as a salt containing the novel phosphoranimine cation
[DMAPPCl2 =NSiMe3 ]+ ([10]+ ) (Scheme 10).75
Fig. 5 Molecular structure of [10][OTf] with thermal ellipsoids at the 50%
probability level. Hydrogen atoms are omitted for clarity (reprinted with
permission from ref. 75. Copyright 2004 American Chemical Society).
4368 | Dalton Trans., 2008, 43634371
Scheme 10
Interestingly, DMAP reacted with 10 in the absence of a halide
abstractor to quantitatively yield [10]Cl. In the solid state this
species slowly reconverts back to 10 and free DMAP over a
period of two weeks at room temperature. The reaction can be
reversed by redissolution in CH2 Cl2 . This phenomenon indicated
the presence of an equilibrium between the product and the
reagents (Scheme 11).75
Scheme 11
Other nitrogen-donor ligands for N-donor-stabilised
N-silylphosphoranimine cations
Since the employment of DMAP for the stabilisation of phos-
phoranimine cations had proven to be successful (both in the
presence or absence of AgOTf), we explored the analogous
chemistry employing the weaker nitrogen donors pyridine (py),
4,4 -bipyridine (bipy) and non-aromatic quinuclidine (quin).
The alkoxy-substituted phosphoranimine Br(CF3 CH2 O)2 P=
NSiMe3 (12) reacted with py, bipy and quin in the pres-
ence of AgOTf to yield the new phosphoranimine salts
[LP(OCH2 CF3 )2 =NSiMe3 ][OTf] (L = py [12a]+ , bipy [12b]+ and
quin [12c]+ ) (Scheme 12 and Fig. 6).76
No reaction was observed between 10 and the aromatic bases
py and bipy in the absence or presence of AgOTf, however in
This journal is The Royal Society of Chemistry 2008
 Scheme 12
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Fig. 6 Molecular structure of [12b][OTf] with thermal ellipsoids at the
50% probability level. Hydrogen atoms are omitted for clarity (reprinted
with permission from ref. 76. Copyright 2007 American Chemical Society).
the reaction with quin an unexpected cationic amino-substituted
phosphoranimine 13 was obtained76 (Scheme 13).
Scheme 13
Synthesis and characterisation of P-donor-stabilised
N-silylphosphoranimine cations
Phosphine-mediated dehalogenation of Cl3 P=NSiMe3 (10)
As shown above, strong N-donor species (DMAP and quin)
stabilise the phosphoranimine cation [Cl2 P=NSiMe3 ]+ . In an effort
to diversify the chemistry of phosphoranimine cations, we decided
to explore the formation of cations stabilised by P-donor ligands.
However, we found that reactions between 10 and R3 P (R = n Bu
or Ph) yield the unexpected N-(phosphino)-phosphoranimines,
R3 P=NPCl2 (R = n Bu 14a; Ph 14b) as a nal reaction product
(Scheme 14).75,77
This journal is The Royal Society of Chemistry 2008
Scheme 14
Intrigued by this result, we investigated the mechanism of this
unusual transformation. We tentatively proposed the following
sequence of reactions which rationalises the formation of N-
(phosphino)phosphoranimines and dichlorophosphoranes from
10 and the tertiary phosphines n Bu3 P and Ph3 P (Scheme 15).
Scheme 15
In this proposed mechanism, the tertiary phosphine induces
a reductive dechlorination of 10 to yield 15 and the transient
chlorophosphinimine 16. The dichlorophosphorane 15 then reacts
with an additional equivalent of 10 to yield an unsymmetrically
substituted bisphosphonioammonium chloride salt 17 which
further reacts with an additional equivalent of tertiary phosphine
undergoing a second dechlorination step to generate the nal
products 14 and 15.77
Synthesis and characterisation of phosphorus-donor-stabilised
N-silyl(halogeno)phosphoranimine cations
The aforementioned results indicated that a presence of a
trichloro-functionality at phosphorus in the phosphoranimine
was incompatible with the preparation of the desired donor
stabilised P(III)P(V) cationic species. Therefore, we decided to
extend our studies to the monohalogenoorganophosphoranimines
BrR2 P=NSiMe3 (R = Me 18; CF3 CH2 O 12) with P-donor ligands.
31
P{1 H}NMR analysis showed that the treatment of 18 and 12
(R = Me, d = 10 ppm; R = CF3 CH2 O, d = 34 ppm) with
R3 P (R = n Bu, d = 30 ppm; R = Me, d = 60 ppm) in
CHCl3 resulted in the formation of new products detected by two
doublets, which were identied as the novel phosphine-stabilised
cationic phosphoranimine salts [Me3 PPR2 =NSiMe3 ]Br (R = Me
19a (Fig. 7); CF3 CH2 O 19b) and [n Bu3 PPR2 =NSiMe3 ]Br (R =
Me 20a; CF3 CH2 O 20b) (Scheme 16).29
Development of an ambient temperature polymerisation of
P-bromo(alkyl/aryl)phosphoranimines to yield
poly(alkyl/aryl)phosphazenes
In an attempt to extend this new chemistry to phosphoranimine
cations with phosphites instead of phosphines as a P-donor ligand,
Dalton Trans., 2008, 43634371 | 4369
 Table 2 Molecular weight data for polymer 24
(RO)3 P (Monom./phosph.)/mol mol1 Solv.
(MeO)3 P 1 CDCl3
(MeO)3 P 10 CDCl3
(MeO)3 P 1 THF
(MeO)3 P 1 Toluene
(EtO)3 P 1 CDCl3
(PhO)3 P 1 CDCl3
a
Time required for 100% conversion at 0.5 M. b 0.1% [n Bu4 N]Br (w/w) in THF eluent. Estimated versus polystyrene standards. c PDI = polydispersity
index (M w /M n ).
Published on 23 July 2008 on http://pubs.rsc.org | doi:10.1039/B719361K
Downloaded by Cinvestav IPN on 11 September 2012
+
Fig. 7 Molecular structure of [19] with thermal ellipsoids at the 30%
probability level. Hydrogen atoms and the bromide counteranion are
omitted for clarity (reprinted with permission from ref. 29. Copyright
2006 American Chemical Society).
Scheme 16
we treated the phosphoranimine 18 with (Me3 O)P. Surprisingly,
the analysis by 31 P{1 H}NMR after 4 h in CH2 Cl2 at room
temperature showed the quantitative formation of the known
polyphosphazene [Me2 P=N]n (21) (d = 7 ppm) instead of the
salt [(Me3 O)PPMe2 =NSiMe3 ]Br (22). The polyphosphazene was
isolated in good yield as a brous solid by precipitation into
pentane (for an example of a solvent cast lm see Fig. 8). Mea-
surements by dynamic light scattering showed that the molecular
weight was high (Rh = 6.8 nm). We also explored the generality of
the reaction using different substituted bromophosphoranimines
(Scheme 17).29
Fig. 8 Film of polyphosphazene 21 (left) and 24 after isolation by
precipitation into pentane (right).
To provide and additional insight, we also proceeded to perform
the polymerisation of 23 by employing different phosphites,
solvents and reaction times. High molecular weight polymer
4370 | Dalton Trans., 2008, 43634371
Time/ha M w ( 105 )/g mol1 b
PDIc
3 4.81 1.68
4 8.22 1.69
4 2.11 3.69
8 1.48 1.94
2 1.47 2.05
48 4.42 6.50
Scheme 17
was obtained in all the cases (Table 2). The mechanism of this
polymerisation is now under investigation in our laboratory.
Summary
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-
nities for the synthesis of polyphosphazene homopolymers and
block copolymers and should provide additional momentum to
the further development this interesting eld.
Acknowledgements
We thank our collaborators on relevent parts of the work
described in this article namely, Christopher A. Reed (University
of California at Riverside) and Harry R. Allcock (Penn State
University). V.B. thanks the States of Jersey for a Postgraduate
Scholarship. A.P. thanks the European Union for a Marie Curie
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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