The first linear multiphosphazene having five different types of side groups and its use as the core of a dendrimeric species

Article abstract of DOI:10.1002/chem.200204630

The step-by-step synthesis of the first oligophosphazenes having more than two types of side functions is described. These multifunctionalized oligophosphazenes possess up to four phosphazene linkages and up to four types of functional side groups. These

Full text of DOI:10.1002/chem.200204630

A.-M. Caminade, J.-P. Majoral et al.
Chem. Eur. J. 2003, 9, 2151 2159
DOI: 10.1002/chem.200204630
¹ 2003 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
2151

FULL PAPER
The First Linear Multiphosphazene Having Five Different Types of Side
Groups and Its Use as the Core of a Dendrimeric Species
Germinal Magro, Bruno Donnadieu, Anne-Marie Caminade,* and Jean-Pierre Majoral*[a]
Abstract: The step-by-step synthesis of the first oligophosphazenes having more
than two types of side functions is described. These multifunctionalized oligophos-
phazenes possess up to four phosphazene linkages and up to four types of functional
side groups. These compounds may serve as models for a better understanding of
electronic delocalization phenomena in linear inorganic chains, and constitute novel
cores for the synthesis of new dendrimeric species possessingseveral types of
functions as end groups, at the level of the core, and within the branches.
Keywords: alkylation
¥
azides
¥
¥
chain structures
phosphazenes
¥ dendrimers
We report here the first examples of a series of perfectly
Introduction
ˆ
defined oligophosphazenes possessing up to four P N link-
The phosphazene linkage plays a key role in several aspects of
ages and five different types of substituents on the phosphorus
atoms, four of them beingdifferent functional groups, as well
as their use for the grafting of two dendrons in a specific
location on the oligophosphazene linkage.
chemistry, in particular for the construction of inorganic
[2]
polymers[1] and strongbases.
Linear polyphosphazenes
ˆ
([-N PR2-]n) have many applications, for instance as flame-
retardants, electrolytes in batteries, or biomedically important
materials.[3] The structural diversity of polyphosphazenes is
enormous; in addition to the general cases in which the R
substituents are the same alongthe chain, polyphosphazenes
that possess two types of substituents, placed either at specific
sites ([-N PRR'-]n) or at random (([-N PR2-]x[-N PR'2-]y)n)
are known, as well as some examples of compounds that have
three or even four side groups, generally consisting of block
Results and Discussion
The only way to obtain a well-defined and specifically
functionalized oligomer is by creating it by means of a step-
by-step process. To build the oligophosphazene backbone, we
chose to use the three-step process that we have already
applied for the internal functionalization of dendrimers.[9] The
first step is a Staudinger reaction between a thiophosphory-
ˆ
ˆ
ˆ
[4]
ˆ
ˆ
copolymers (([-N PRR'-]x[-N PR''R'''-]y)n). On the other
hand, small and well-defined oligophosphazenes (linear chain
ˆ
ˆ
ˆ
of three or four P N linkages) are less well known, and their
structural diversity is limited. To the best of our knowledge,
only one example of a defined oligomer possessing at least
lated azide and a phosphine to create a P N-P S linkage. The
ˆ
second step is an alkylation of the P S group with alkyl
À
triflates to induce a weakeningof the P S bond. The third step
ˆ
three linearly alternatingP N linkages and at least two types
of substituents on phosphorus was previously described,
is the desulfurization reaction with P(NMe2)3 to generate a
tricoordinate phosphorus atom that is able to react in a
Staudinger reaction. We have already demonstrated the
feasibility of the three steps; however, we never tried to
repeat them several times. Furthermore, these reactions were
carried out either in the absence of any functional group on
the dendrimer, or in the presence of an aldehyde as the sole
functional group.
Thus, the first crucial point for the multistep buildingof
oligophosphazenes is the choice of the functionalized azides,
since the functional groups must not react during the multi-
step process, particularly when alkyl triflates are used. We
already knew that the aldehyde groups are compatible, but we
needed to check several other groups. For this purpose, we
[5]
ˆ
ˆ
ˆ
namely P3N3F5-N PF2-N PCl2-N PCl3.
Such inorganic oligomers might also be used as a tool for a
better understandingof the bondingin polyphosphazenes;
however, it might also be used as a novel core for a
dendrimeric species. Indeed, the grafting of one,[6] two,[7] or
a large number[8] of dendrons to organolinear oligomers or
polymers was previously reported, but there is no example of
dendrons grafted to a linear inorganic and multifunctionalized
oligomer.
[a] Dr. A.-M. Caminade, Dr. J.-P. Majoral, Dr. G. Magro, B. Donnadieu
Laboratoire de Chimie de Coordination CNRS
205 route de Narbonne, 31077 Toulouse Cedex 4 (France)
Fax : (‡33)5-61-55-30-03
ˆ
built several R3P N-P(S)(OAr)2 models, and tested their
reactivity. Arylnitride, arylmalonitrile, and azobenzene
E-mail: caminade@lcc-toulouse.fr, majoral@lcc-toulouse.fr
2152
¹ 2003 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
DOI: 10.1002/chem.200204630
Chem. Eur. J. 2003, 9, 2151 2159

Multifunctional Linear Multiphosphazenes
2151 2159
Table 1. 31P{1H} NMR data (d; 2J[Hz]) in CDCl3.
Compound
P0
J(P0,P1)
P1
J(P1,P2)
P2
J(P2,P3)
P3
J(P3,P4)
P4
P5
J(P5,P'5)
P'5
P6
2-(PN)1
3-(PN)1
4-(PN)1
2-(PN)2
3-(PN)2
4-(PN)2
2-(PN)3
3-(PN)3
2-(PN)4
6-G1
15.3
23.2[a]
12.9
15.8
20.0
14.8
16.2
18.4
16.6
30.1
20.2
56.7
23.8
26.1
25.0
23.0
26.1
24.1
50.3
23.4[b]
144.8
À 14.6
À 17.2
À 11.9
À 16.3
À 16.3
À 16.4
58.1
54.8
78.0
52.3
55.5
54.4
46.9
22.2
137.0
À 17.8
À 19.1
À 19.7
55.5
55.9
53.7
45.0
20.8
À 20.9
56.6
57.2
46.5
46.4
11.9
18.7
18.2
30.5
33.2
34.2
53.1
52.4
52.4
61.6
61.6
61.6
7-G1
8-G2
16.3
25.0
À 16.3
54.1
À 18.8
54.9
À 20.2
[a] Or P1. [b] Or P0.
groups do not react with alkyl triflates. Therefore, they could
be used as functional groups at any step. On the other hand,
aryldimethylamino groups are partly alkylated (as expected)
and thus, they could be used only in the last step of the
construction. The second crucial point concerns the tricoor-
dinate phosphorus atom generated during the desulfurization
process: it must not weaken the structure. The arylmalonitrile
group was eliminated from our selection because it induces
such a problem.
Havingcarried out these preliminary experiments, we
began the synthesis of the oligophosphazene. The first step
is the Staudinger reaction between triphenylphosphine and
the thiophosphinoazide 1a to give the thiophosphorylated
monophosphazene 2-(PN)1 in quantitative yield (Scheme 1).
pentane (1/20) (Table 2). The X-ray crystal structure of 2-
(PN)1 is shown in Figure 1.[10]
The second step of the construction of the oligophospha-
zene is the methylation of the thiophosphoryl group with
CF3SO3Me to afford compound 3-(PN)1 in very good yield.
The 31P NMR spectrum of 3-(PN)1 consists of an AB system at
d ˆ 23.2 23.4 ppm. Thus, the alkylation induces a shieldingof
the signal corresponding to the thiophosphoryl group (Dd ˆ
À27), as expected, but also a deshieldingof the singal
correspondingto the PPh 3 group (Dd ˆ 8). Single crystals of 3-
(PN)1 were obtained from chloroform (Table 2). The X-ray
crystal structure of 3-(PN)1 is shown in Figure 2.[10]
Compounds 2-(PN)1 and 3-(PN)1 differ only by the
presence of the methyl group linked to S in 3-(PN)1, thus it
is interestingto note the structural variations induced by the
À
alkylation (Table 3): it induces a lengthening of the P S bond,
N
N
N
C
C
C
Table 2. X-ray data for 2-(PN)1 and 3-(PN)1.
Ph3P
+
Me
O
P
O
P
O
P
S
2-(PN)1
3-(PN)1
i)
ii)
C
N
O
P
P N
S
P N
S
P N
2
-N2
formula
fw
C32H23N3O2P2S
575.53
C34H26F3N3O5P2S2
739.64
N3
CF SO
3
O
O
3
O
1a
crystal dimensions[mm]
0.45 Â 0.50 Â 0.12
monoclinic
P21/n
11.6605(11)
8.4315(6)
28.816(3)
97.694(12)
2807.6(4)
4
0.50 Â 0.37 ÂÂ 0.15
monoclinic
P21/c
11.7970(9)
13.6570(12)
21.1917(15)
95.452(9)
3398.8(5)
4
2-(PN)1
3-(PN)1
4-(PN)1
C
C
N
C
crystal system
space group
a[ä]
b[ä]
c[ä]
N
N
Scheme 1. The first three steps for the buildingof the oligophosphazenes.
i) CF3SO3Me; ii) P(NMe2)3, À[MeSP(NMe2)3][CF3SO3].
b[8]
V[ä]
Z
The 31P NMR spectrum of 2-(PN)1 consists of two doublets
2
ˆ
at d ˆ 15.3 (PPh3) and 50.3 ppm (P S) with J(P,P) ˆ 30.1 Hz
1calcd [gcmÀ3
]
1.362
0.265
1192
1.445
0.314
1520
(Table 1). Single crystals of 2-(PN)1 were obtained from THF/
m[mmÀ1
F000
]
l[ä]
2qmax [8]
T[K]
0.71073
52.3
160(2)
0.71073
52.5
180(2)
¡
¬
¬
Abstract in French: La synthese etape par etape des premiers
¡
¬
oligophosphazenes ayant plus de deux fonctions laterales
scan mode
f rotation
21171
5525
f rotation
33037
6671
¬
¬
¡
differentes est decrite. Ces oligophosphazenes plurifonction-
nalises possedent jusqu×a 4 liaisons phosphazõne et 4 types de
groupements fonctionnels lateraux. Ces composes peuvent
no. of reflections collected
no. of unique reflections
no. of variables
absorption correction
Tmin Tmax
¬
¡
¡
361
443
¬
¬
semiempirical
0.556 0.864
1.029
semiempirical
0.524 0.851
1.026
¡
¬
servir de modeles pour une meilleure comprehension des
GOF on F 2
¬
¡
¬
¬
phenomenes de delocalisation electronique dans des chaÓnes
R1 (all data)
WR2 (all data)
R1 (I > 2s(I))
WR2 (I > 2s(I))
1max, 1min
0.0499
0.0858
0.0332
0.0799
0.0654
0.1067
0.0406
0.0961
¬
inorganiques lineaires, et ils constituent des c˙urs originaux
¡
¡
¬
pour la synthese de nouvelles especes dendrimeriques ayant
plusieurs types de fonctions en surface, au niveau du c˙ur et
dans les branches.
0.269, À0.864
0.613, À0.354
Chem. Eur. J. 2003, 9, 2151 2159
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A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
Table 3. Bond lengths [ä] and angles [8] for the P2 N3 P1(
O C)2 S
fragment of 2-(PN)1 and 3-(PN)1, and variations between both structures.
Parameter
2-(PN)1
1.9267(6)
1.5734(14)
1.5806(15)
1.6308(12)
1.6146(14)
1.386(2)
3-(PN)1
2.0397(9)
1.5370(19)
1.5951(19)
1.5726(18)
1.5749(17)
1.407(3)
D2-(PN)1 ! 3-(PN)1
À
P1 S
‡ 0.113
À 0.036
‡ 0.014
À 0.058
À 0.040
‡ 0.022
‡ 0.026
À 6.0
À
P1 N3
À
N3 P2
À
P1 O1
À
P1 O2
À
O1 C1
À
O2 C2
1.384(2)
123.24(6)
134.67(10)
1.410(3)
117.20(8)
137.65(13)
N3-P1-S
P1-N3-P2
‡ 3.0
as expected, but it also induces a slight shortening of the
À
À
N P(S) bond and a slight lengthening of the Ph3P N bond.
This indicates at least a partial delocalization of the charge
alongthe inoragnic backbone of
3-(PN)1. There is also a
À
Figure 1. Structure of compound 2-(PN)1 (ORTEP drawing; hydrogen
atoms are omitted for clarity).
shorteningof the P OAryl bonds in 3-(PN)1.
The third step of the construction of the oligophosphazene
À
consists in breakingthe P S bond to obtain a tricoordinate
phosphorus atom (PIII). Reaction of 3-(PN)1 with P(NMe2)3
À
induces the transfer of the S Me group and leads to 4-(PN)1
(Scheme 1). This compound is very sensitive to oxidation, thus
it was not isolated but only characterized by 31P NMR
spectroscopy. It has a very characteristic value of the chemical
2
shift, namely d ˆ 144.8 ppm (d, J(P,P) ˆ 56.7 Hz) for the PIII
center.
The sequence of three reactions can be repeated starting
with 4-(PN)1. Indeed, the tricoordinate phosphorus atom of 4-
(PN)1 reacts readily with the azide 1b to afford the
diphosphazene 2-(PN)2 that contains two nitrile and two
azobenzene functional groups[11] (Scheme 2). The methylation
of 2-(PN)2 gives the expected 3-(PN)2, which is desulfurized
by P(NMe2)3 to afford 4-(PN)2. A third cycle of reactions can
begin with 4-(PN)2 and the azide 1c to afford 2-(PN)3. To the
best of our knowledge, this compound is the first linear
triphosphazene possessingthree types of functional groups.
The three-step cycle can be applied again, starting from 2-
(PN)3. The azide 1d is reacted in the last step to afford 2-
(PN)4, the first tetraphosphazene functionalized by four
Figure 2. The cationic part of compound 3-(PN)1 (ORTEP drawing;
hydrogen atoms are omitted for clarity).
N
N
N
O
N
N
i)
N
N
C
CHO
N
N
C
C
S
S
CF3SO3
O
N
P
CHO
O
P
2
N
N3
N3
O
O
P
O
P
O
P
O
O
P
2
1c
1b
ii)
4-(PN)1
4-(PN)2
P N
N P
O
S
P N
N
S
N
P
P N
N P
O
S
Me
O
O
O
O
O
2-(PN)2
3-(PN)2
2-(PN)3
C
N
C
N
CHO
N
N
C
N
N
N
N
N
N
O
N
N
N
CHO
C
N
N
CHO
C
S
NMe2
NMe2
P O
CF3SO3
O
P
N3
O
P
O
P
O
O
O
P
NMe2
2
i)
1d
ii)
P N
N
P N
N P
O
N
N
P
S
N
P S
O
4-(PN)3
Me
O
O
O
O
O
C
3-(PN)3
CHO
N
2-(PN)4
N
C
N
CHO
N
N
N
Scheme 2. Repetitive multistep synthesis of the tetraphosphazene 2-(PN)4. i) CF3SO3Me; ii) P(NMe2)3, À[MeSP(NMe2)3][CF3SO3].
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2154

Multifunctional Linear Multiphosphazenes
2151 2159
different types of functions (nitrile, azobenzene, aldehyde,
and amine) (Scheme 2). Accordingto our previous experi-
ments, the use of the azide 1d precludes the continuation of
the growth of the phosphazene chain because the NMe2
groups will react during the alkylation step.
All these mono-, di-, tri-, and tetraphosphazenes are
characterized by multinucleus NMR and mass spectrometry
(FAB); however, the most important tool is 31P NMR
spectroscopy (Table 1). As an illustration, Figure 3 gives the
31P NMR spectrum of compound 2-(PN)4, as well as its
simulated spectrum, which is in perfect agreement with the
real one. The spectrum is complex, as expected, but all the five
phosphorus atoms can be precisely identified.
Figure 4. Variation of the 31P NMR chemical shifts of all phosphorus atoms
for compounds 2-(PN)1 to 2-(PN)4 and 3-(PN)1 to 3-(PN)3.
(PN)4 and from 3-(PN)1 to 3-(PN)3. The behavior of the P0
atom is totally different from that of P1, P2, and P3 atoms.
Indeed, the chemical shifts of the latter vary from d ꢀ 50 ppm
ˆ
in the P S form (2-(PN)x) to ꢀ24 ppm in the P-S-Me form (3-
ˆ
(PN)x) and ꢀ À 15 ppm in the P N form (2-(PN)x‡1). Their
chemical shift values remain almost constant for all the
subsequent reactions. In marked contrast to such behavior,
the chemical shift value of P0 varies at each step of the
oligophosphazene construction. It oscillates around d ˆ 17
with progressively decreasing amplitude when the alkylation
site is remote. The phenomenon remains sensitive, even for
the 2-(PN)3 ! 3-(PN)3 reaction that occurs seven bonds away
from P0. Thus, this data suggests that the charge introduced
duringthe alkylation step is delocalized throuhgout the
inorganic phosphazene chain; however, with a decreasing
effectiveness as the site of alkylation moves away from the
beginning of the chain.
Figure 3. a) 31P NMR spectrum of the tetraphosphazene 2-(PN)4. b) Si-
mulated 31P NMR spectrum of 2-(PN)4.
Such a series of compounds offers a very unique oppor-
tunity to study the possibility of an electronic delocalization
In addition to this novel property, the other important
feature of compound 2-(PN)4 is the presence of four types of
functional groups. Because no well-defined inorganic oligom-
er was used as a dendrimer core up to now, we decided to test
this compound. The aldehyde groups appear to be the most
compatible with the chemistry of our dendrimers. Thus, we
designed dendron 7-G1, that has a N,N-disubstituted hydra-
zine core and trifluoro-p-cresol end groups. This compound
was synthesized by an adaptation of the procedure we had
already reported for the synthesis of dendrons.[15] Starting
from dendron 5-G1, four equivalents of the sodium salt of
trifluoro-p-cresol were reacted with the P(S)Cl2 end groups,
leadingto dendron 6-G1; then methyl hydrazine was reacted
with the core to give dendron 7-G1. The condensation reaction
between two equivalents of dendron 7-G1 and the tetraphos-
phazene 2-(PN)4 occurs readily to afford the dendrimeric
species 8-G2, which was isolated in very good yield (95%)
after workup (Scheme 3). The condensation reaction is
alongan inorganic chain. Indeed, it is obvious that the
p
system in oligo- or polyphosphazenes is very different from
that of organic polymers. A study of the electronic structure of
oligophosphazenes by means of density functional theory
(DFT) calculations suggested that the p bondingis induced by
a negative hyperconjugation that involves electron donation
from the lone pair p (N) orbitals to the s* (P X) orbitals[12]
(X ˆ substituent); such delocalization is mostly confined in
the vicinity of the P-N-P region, the so-called ™island p
bonding∫.[13] Thus, the possibility of delocalization through
several phosphazene linkages is an open question. The
presence of a charge and the structural modification that it
induces could help to answer this question. A few charged,
small oligophosphazenes were previously reported,[14] but
ˆ
their symmetrical structure was not adequate ([R3P N-
‡
‡
ˆ
ˆ
ˆ
PR2 N-PR3] is equivalent to [R3P-N PR2-N PR3] ). On
the other hand, the series of oligophosphazenes studied here
could help to answer this question using 31P NMR spectro-
scopy, which is again the best tool to characterize such
behavior. Indeed, the chemical shift of the phosphorus atom
of the Ph3P group at the beginning of the chain (noted P0) is
sensitive to the alkylation that occurs on sulfur. Figure 4
displays the variation of the chemical shift value of all
phosphorus atoms for each compound from 2-(PN)1 to 2-
1
characterized in H NMR by the disappearance of the signal
correspondingto the aldehyde groups. Compound 8-G2 was
also characterized by 31P NMR spectroscopy: in addition to
the signals corresponding to the tetraphosphazene chain,
three series of signals (two doublets and one singlet) appear
(Table 1). The condensation is also confirmed by a slight
shieldingof the doublet correspondingto the PPh group of
2
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A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
dehyde functions gave rise to an unusual type of dendrimeric
species with a multifunctionalized oligophosphazene core and
eight trifluoromethyl groups as end groups, linked to the
oligophosphazene chain through phosphazene linkages. Ob-
viously, these methods of synthesis could be applied to other
functions (at the core or on the surface), to vary the potential
uses of such compounds.
S
Me
N
S
O
P
H
C
N
P Cl
P
P
P
N
N
N
2
2
5-G1
NaO
Me
CF3
S
P
S
P
H
C
O
CF3
CF3
O
N
N
2
2
6-G1
MeNHNH2
S
P
Me
N
S
P
H
C
Experimental Section
CF3
O
Me
N
O
2
2
N
H2N
All manipulations were carried out with standard high-vacuum and dry-
argon techniques. The solvents were freshly dried and distilled (THF and
ether over sodium/benzophenone, pentane and CH2Cl2 over phosphorus
pentoxide, toluene over sodium); they were degassed prior to use in the case
of experiments that used derivatives with tricoordinate phosphorus atoms.
All compounds that contained azo groups were protected against light during
7-G1
O
S
P
Me
N
2-(PN)4
O
CF3
CF3
N
CH
O
H
S
O
P
O
N
C
Me
N
N
N
Me
P
1
P
manipulation to avoid the isomerization of these bonds. H, 13C, 31P NMR
N
S
N
O
spectra were recorded with Bruker AC200, AC250, DPX300, or AMX400
CH
O
P
O
N
N
C
spectrometers. References for NMR chemical shifts were 85% H3PO4 for 31
P
NMe2
NMR, SiMe4 for H and 13C NMR, CF3CO2H for 19F NMR. The 13C NMR
signals were assigned on the basis of Jmod, two-dimensional HMBC, and
HMQC, broad-band or CW 31P decouplingexperiments, when necessary. The
numberingused for NMR assignments is depicted in Scheme 4. The program
MestRe-C was used to generate the simulated spectra. Mass spectra (FAB)
were recorded on a Finnigan Mat TSQ700. Compounds 1a,[15] 1c,[16] 1d,[15]
and the first-generation dendron 5-G1[15] were synthesized as described
previously. All 31P NMR data are gathered in Table 1.
1
CF3
O
O
O
P N
N
N
N P
P
P
S
O
O
O
CF3
NMe2
N
C
CH N
N
N
O
P
Me
N
S
O
S
O
N
P
Me
N
C
N
O
P
H
CF3
CF3
Compound 1b: A solution of 4-hydroxyazobenzene (0.39 g, 1.97 mmol)
and NEt3 (0.275 mL, 1.97 mmol) in THF (20 mL) was stirred for 30 min.
This mixture was added dropwise at À1008C to a solution of trichlor-
ophosphine sulfide (0.1 mL, 0.985 mmol) in THF (10 mL). The resulting
mixture was slowly allowed to reach room temperature, and was then
stirred for 12 h at this temperature. The mixture was filtered to eliminate
the precipitated triethylamine hydrochloride. The resultingsolution was
evaporated to dryness. The residue was dissolved in acetone (20 mL), and
sodium azide (64 mg, 0.985 mmol) was added. This solution was stirred for
24 h at room temperature, and then evaporated to dryness. THF (20 mL)
was added to the residue, and the mixture was centrifuged to eliminate
sodium chloride. The resultingsolution was evaporated to dryness to yield
an oily orange liquid that was purified by column chromatography on silica
(AcOEt/Hexane: 3/7). Compound 1b was obtained as a waxy orange oil in
32% yield. 31P{1H} NMR (CDCl3): d ˆ 58.8 ppm (s); 1H NMR (CDCl3):
d ˆ 7.41 (dd, 3J(H,H) ˆ 8.8 Hz, 4J(H,P) ˆ 1.9 Hz, 4H; HC2), 7.44 7.58 (m,
6H; HC7, HC8), 7.92 (dd, 3J(H,H) ˆ 8.1 Hz, 4J(H,H) ˆ 1.7 Hz; HC6),
7.98 ppm (dd, 3J(H,H) ˆ 8.8 Hz, 5J(H,P) ˆ 0.9 Hz, 4H; HC3); 13C{1H}
NMR (CDCl3): d ˆ 121.7 (d, 3J(C,P) ˆ 4.4 Hz, C2), 122.8 (s, C6), 124.3 (s,
C3), 129.0 (s, C7), 131.1 (s, C8), 150.3 (d, 5J(C,P) ˆ 2.9 Hz, C4), 151.4 (d,
2J(C,P) ˆ 8.8 Hz, C1), 152.3 ppm (s, C5); IR (KBr): nÄ ˆ 2150 cmÀ1 (N3);
elemental analysis calcd (%) for C24H18N7O2PS (499.5): C 57.71, H 3.63, N
19.63; found: C 57.63, H 3.58, N 19.51.
CH
N
O
S
N
8-G2
P
O
Me
CF3
Scheme 3. Regioselective grafting of two dendrons on the oligophospha-
zene 2-(PN)4.
the dendron from d ˆ 18.7 ppm for 7-G1 to d ˆ 18.2 ppm for 8-
G2. This very novel dendrimeric species possesses several
types of functional groups at the core, in the branches, and on
the surface, and consists of phosphazene linkages not only at
the core but also within the branches.
Conclusion
We have demonstrated, for the
first time, the possibility of
buildinga series of oligophos-
Cp'
Cm'
Co'
Co'
8
phazenes that contain up to
four different functionalized
side groups that can be precise-
ly placed on the backbone.
These compounds were found
to be useful for a better under-
standingof the delocalization
effects in inorganic chains, but
also as a novel core of dendri-
meric species. Indeed, the con-
densation reaction of two
equivalents of dendrons on al-
7 C2
C2
2
3
CH3
C5 C5
P5
CH3
N
N
6
4
1
C2
C5
C
H
N
N
P6
P'5 O C5
5
Ph
C2
N
4
1
C6
O C6
C6
CF3
S
2 C6
N
N
3
S
CH3
N
C
HC
4
N
4
4
4
C4
C1
C3
3 C2
3
CH3
3
5
6
3
2
C4
C2
C2
C3
C3
C4
C1
C1
2
2
2
C4
1
C4
1
1
1
C3
C4
O
C1
O
C2
O
Cm
Co
O
Cp
Ci P0
N
P1
N
P2
N
P3
N
P4
S
Scheme 4. Numberingscheme used for the NMR assignments
www.chemeurj.org
2156
¹ 2003 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2003, 9, 2151 2159

Multifunctional Linear Multiphosphazenes
2151 2159
Compound 2-(PN)1: A solution of 1a (0.288 g, 0.845 mmol) in dichloro-
methane (3 mL) was added to a solution of triphenylphosphine (0.233 g,
0.888 mmol) in dichloromethane (3 mL) at room temperature. This
solution was stirred for 12 h, and then evaporated to dryness. The resulting
powder was washed three times with THF/pentane (1/20) to give 2-(PN)1 as
a white powder in 99% yield. Single crystals suitable for X-ray diffraction
were obtained by slow evaporation at room temperature in a mixture of
THF/pentane (1/20). 1H NMR (CDCl3): d ˆ 7.23 (d, 3J(H,H) ˆ 8.0 Hz, 4H;
(CDCl3): d ˆ À2.0 ppm (s, CF3); IR (KBr): nÄ ˆ 2225 cmÀ1 (CN); elemental
analysis calcd (%) for C58H44F3N8O7P3S2 (1179.1): C 59.08, H 3.76, N 9.50;
found: C 59.21, H 3.85, N 9.44.
Compound 4-(PN)2: HMPT (32 mL, 0.174 mmol) was added dropwise at
room temperature to a solution of 3-(PN)2 (0.205 g, 0.174 mmol) in CH2Cl2
(3 mL). The solution was stirred for 2 h, and then evaporated to dryness.
The residue was extracted with toluene, then the solution was evaporated
to dryness to afford 4-(PN)2 as a highly air-sensitive orange powder in 72%
yield.
2
C1 H), 7.40 7.65 ppm (m, 19H; Harom); 13C{1H} NMR (CDCl3): d ˆ 107.9 (s,
C1 ), 118.6 (s, CN), 122.5 (d, 3J(C,P) ˆ 5.4 Hz, C1 ), 128.8 (dd, 1J(C,P) ˆ
4
2
106.0 Hz, 3J(C,P) ˆ 3.7 Hz, Ci), 128.9 (d, 3J(C,P) ˆ 13.9 Hz, Cm), 132.7 (d,
Compound 2-(PN)3: A solution of 1c (0.061 g, 0.174 mmol) in THF (5 mL)
2J(C,P) ˆ 9.7 Hz, Co), 133.2 (d, 4J(C,P) ˆ 3.5 Hz, C1 ), 133.6 (s, Cp),
3
was added at room temperature to
a solution of 4-(PN)2 (0.171 g,
1
155.3 ppm (d, 2J(C,P) ˆ 10.1 Hz, C1 ); IR (KBr): nÄ ˆ 2225 cmÀ1 (CN);
0.174 mmol) in THF (5 mL). The solution was stirred for 12 h, and then
evaporated to dryness. The resultingpowder was washed three times with
THF/pentane (1/20) to afford 2-(PN)3 as an orange powder in 83% yield.
1H NMR (CDCl3): d ˆ 7.10 (dd, 3J(H,H) ˆ 8.7 Hz, 4J(H,P) ˆ 0.9 Hz, 4H;
elemental analysis calcd (%) for C32H23N3O2P2S (575.6): C 66.78, H 4.03, N
7.30; found: C 66.73, H 3.99, N 7.25.
Compound 3-(PN)1: Methyl triflate (40 mL, 0.35 mmol) was added drop-
wise at room temperature to a solution of 2-(PN)1 (0.201 g, 0.35 mmol) in
CH2Cl2 (2 mL). The resultingsolution was stirred for 20 min, and then
evaporated to dryness. The residue was washed three times with THF/
pentane (1/20) to give 3-(PN)1 as a white powder in 95% yield. Single
crystals suitable for X-ray diffraction were obtained by slow evaporation at
room temperature in chloroform. 1H NMR (CDCl3): d ˆ 2.53 (d, 3J(H,P) ˆ
17.3 Hz, 3H; S-CH3), 7.25 7.62 ppm (m, 23H; Harom); 13C{1H} NMR
HC1 ), 7.15 (dd, 3J(H,H) ˆ 8.8 Hz, 4J(H,P) ˆ 0.9 Hz, 4H; HC2 ), 7.28 (dd,
2
2
2
3J(H,H) ˆ 8.4 Hz, 4J(H,P) ˆ 0.9 Hz, 4H; HC3 ), 7.40 7.63 (m, 25H; Harom),
3
3
7.67 (d, 3J(H,H) ˆ 8.7 Hz, 4H; HC2 ), 7.75 (d, 3J(H,H) ˆ 8.7 Hz, 4H; HC3 ),
3
4
6
7.97 (dd, J(H,H) ˆ 6.9 Hz, J(H,H) ˆ 1.5 Hz, 4H; HC2 ), 9.84 ppm (s, 2H;
4
CHO); 13C{1H} NMR (CDCl3): d ˆ 109.2 (s, C1 ), 118.5 (s, CN), 121.8 (d,
2
2
3J(C,P) ˆ 5.0 Hz, C2 ), 122.2 (d, 3J(C,P) ˆ 5.6 Hz, C1 ), 122.2 (d, 3J(C,P) ˆ
5.1 Hz, C3 ), 123.3 (s, C2 ), 124.4 (s, C2 ), 127.6 (dd, 1J(C,P) ˆ 107.7 Hz,
2
6
3
7
3J(C,P) ˆ 3.9 Hz, Ci), 129.6 (d, 3J(C,P) ˆ 13.2 Hz, Cm), 129.6 (s, C2 ), 131.5 (s,
4
(CDCl3): d ˆ 13.7 (d, 2J(C,P) ˆ 5.1 Hz, S-CH3), 110.7 (s, C1 ), 117.5 (s, CN),
3
8
4
2
3
2
1
C3 ), 131.6 (s, C2 ), 132.8 (s, C3 ), 132.8 (d, J(C,P) ˆ 11.4 Hz, Co), 133.9 (d,
122.0 (d, J(C,P) ˆ 3.6 Hz, C1 ), 123.8 (d, J(C,P) ˆ 112.7 Hz, Ci), 129.7 (d,
3
4
4J(C,P) ˆ 2.9 Hz, CP) , 134.2 (s, C1 ), 149.8 (d, 5J(C,P) ˆ 1.3 Hz, C2 ), 152.9 (s,
3
3J(C,P) ˆ 11.9 Hz, Cm), 132.0 (d, 2J(C,P) ˆ 10.4 Hz, Co), 134.6 (brs, C1 , CP),
5
2
1
2
1
151.8 ppm (d, 2J(C,P) ˆ 9.8 Hz, C1 ) (CF3SO3À not detected); 19F{1H} NMR
1
C2 ), 153.6 (d, J(C,P) ˆ 8.6 Hz, C2 ), 154.5 (d, J(C,P) ˆ 8.8 Hz, C1 ), 157.3
1
(d, 2J(C,P) ˆ 8.8 Hz, C3 ), 191.4 ppm (s, CHO); IR (KBr): nÄ ˆ 1702 (CHO),
(CDCl3): d ˆ À2.0 ppm (s, CF3); IR (KBr): nÄ ˆ 2225 cmÀ1 (CN); elemental
analysis calcd (%) for C34H26F3N3O5P2S2 (739.7): C 55.21, H 3.54, N 5.68;
found: C 55.14, H 3.48, N 5.60.
‡
2228 cmÀ1 (CN). MS (FAB): m/z (%): 1302 (100) [M‡H] ; elemental
analysis calcd (%) for C70H51N9O8P4S (1302.2): C 64.57, H 3.95, N 9.68;
found: C 64.49, H 3.90, N 9.61.
Compound 4-(PN)1: Hexamethylphosphorustriamide (HMPT, 117 mL,
0.64 mmol) was added dropwise at room temperature to a solution of 3-
(PN)1 (0.476 g, 0.64 mmol) in dichloromethane (5 mL). The resulting
solution was stirred for 2 h, and then evaporated to dryness. The residue
was extracted with toluene, then the solution was evaporated to dryness to
afford 4-(PN)1 as a highly air-sensitive white powder (70% yield).
Compound 3-(PN)3: Methyl triflate (4.1 mL, 0.036 mmol) was added
dropwise at room temperature to
a solution of 2-(PN)3 (0.043 g,
0.033 mmol) in dichloromethane (3 mL). The resultingsolution was stirred
for 20 min, and then evaporated to dryness. The residue was washed three
times with CH2Cl2/pentane (1/20). 3-(PN)3 was isolated as an orange
powder in 95% yield. 1H NMR (CDCl3): d ˆ 2.61 (d, 3J(H,P) ˆ 18.3 Hz,
3H; S-CH3), 6.90 7.93 (m, 49H; Harom), 9.82 ppm (s, 2H; CHO); 13C{1H}
Compound 2-(PN)2: A solution of 1b (0.093 g, 0.186 mmol) in THF (5 mL)
was added at room temperature to
a solution of 4-(PN)1 (0.101 g,
4
NMR (CDCl3): d ˆ 13.8 (d, 2J(C,P) ˆ 5.8 Hz, S-CH3), 109.7 (s, C1 ), 117.7 (s,
0.186 mmol) in THF (5 mL). The solution was stirred for 12 h and then
evaporated to dryness to afford an oil, which was purified by column
chromatography on silica (ethyl acetate/pentane (1/4)). 2-(PN)2 was
isolated as an orange oil in 85% yield. 1H NMR (CDCl3): d ˆ 7.07 (dd,
2
3
2
CN), 120.8 (d, 3J(C,P) ˆ 5.8 Hz, C2 ), 121.0 (d, J(C,P) ˆ 5.0 Hz, C1 ), 121.6
3
2
6
3
1
(d, J(C,P) ˆ 5.8 Hz, C3 ), 123.1 (s, C2 ), 124.4 (s, C2 ), 126.4 (dd, J(C,P) ˆ
7
108.3 Hz, 3J(C,P) ˆ 3.5 Hz, Ci), 129.3 (s, C2 ), 129.4 (d, 3J(C,P) ˆ 13.9 Hz,
Cm), 131.7 (s, C2 ), 131.9 (s, C3 ), 132.1 (d, 2J(C,P) ˆ 10.3 Hz, Co), 133.9 (brs,
8
3
4
2
3
3J(H,H) ˆ 8.6 Hz, J(H,P) ˆ 1.3 Hz, 4H; HC1 ), 7.20 (dd, J(H,H) ˆ 8.7 Hz,
3
4
4
2
CP), 134.2 (s, C1 ), 134.6 (s, C3 ), 150.1 (brs, C2 ), 151.6 (d, 2J(C,P) ˆ 8.3 Hz,
4J(H,P) ˆ 1.5 Hz, 4H; HC2 ), 7.39 7.65 (m, 25H; Harom), 7.77 (d, 3J(H,H) ˆ
C3 ), 152.3 (s, C2 ), 153.3 (brd, 2J(C,P) ˆ 11.5 Hz, C2 ), 153.4 (brd, 2J(C,P) ˆ
1
5
1
3
3
4
8.8 Hz, 4H; HC2 ), 7.91 ppm (dd, J(H,H) ˆ 7.5 Hz, J(H,H) ˆ 1.4 Hz, 4H;
1
À
8.1 Hz, C1 ), 190.4 ppm (s, CHO), (CF3SO3 not detected); 19F{1H} NMR
(CDCl3): d ˆ À2.0 ppm (s, CF3); IR (KBr): nÄ ˆ 1701 (CHO), 2227 cmÀ1
(CN); elemental analysis calcd (%) for C72H54F3N9O11P4S2 (1466.3): C
58.98, H 3.71, N 8.60; found: C 58.92, H 3.65, N 8.45.
6
4
HC2 ); 13C{1H} NMR (CDCl3): d ˆ 108.5 (s, C1 ), 118.2 (s, CN), 121.8 (d,
2
3
2
6
3J(C,P) ˆ 4.2 Hz, C2 ), 121.9 (d, J(C,P) ˆ 5.8 Hz, C1 ), 122.8 (s, C2 ), 123.9
3
(s, C2 ), 127.6 (dd, 1J(C,P) ˆ 114.3 Hz, 3J(C,P) ˆ 3.9 Hz, Ci), 129.0 (d,
7
8
3J(C,P) ˆ 13.4 Hz, Cm), 129.1 (s, C2 ), 130.9 (s, C2 ), 132.5 (d, 2J(C,P) ˆ
3
4
5
11.6 Hz, Co), 133.2 (s, CP), 133.6 (s, C1 ), 149.1 (s, C2 ), 152.6 (s, C2 ), 154.1
Compound 2-(PN)4: HMPT (6 mL, 0.034 mmol) was added dropwise at
room temperature to a solution of 3-(PN)3 (0.048 g, 0.033 mmol) in
dichloromethane (3 mL). The solution was stirred for 2 h, and then
evaporated to dryness. The residue was extracted with toluene, and then
the solution was evaporated to dryness. The resultingcompound was not
characterized, but used directly. It was dissolved in THF (5 mL), and then a
solution of 1d (0.0125 g, 0.033 mmol) in THF (5 mL) was added at room
temperature. The resultingsolution was stirred for 12 h, and then
evaporated to dryness to afford a powder that was washed three times
with THF/pentane (1/20). 2-(PN)4 was isolated as an orange powder in
70% yield. 1H NMR (CDCl3): d ˆ 2.78 (s, 12H; NMe2), 6.40 (dd, 3J(H,H) ˆ
(d, 2J(C,P) ˆ 9.9 Hz, C2 ), 154.5 ppm (d, 2J(C,P) ˆ 8.2 Hz, C1 ); IR (KBr):
1
1
nÄ ˆ 2225 cmÀ1 (CN); MS (FAB): m/z (%): 1015 (100) [M‡H] ; elemental
‡
analysis calcd (%) for C56H41N8O4P3S (1015.0): C 66.27, H 4.07, N 11.04;
found: C 66.35, H 4.15, N 10.91.
Compound 3-(PN)2: Methyl triflate (20 mL, 0.177 mmol) was added
dropwise at room temperature to
a solution of 2-(PN)2 (0.177 g,
0.174 mmol) in dichloromethane (2 mL). The resultingsolution was stirred
for 20 min, and then evaporated to dryness, to afford an oil, which was
washed three times with CH2Cl2/pentane (1/20). 3-(PN)2 was isolated as an
orange oil in 95% yield. 1H NMR (CDCl3): d ˆ 2.63 (d, 3J(H,P) ˆ 18.0 Hz,
3
4
2
4
6
4
2
3H; S-CH3), 6.94 (dd, J(H,H) ˆ 8.7 Hz, J(H,P) ˆ 1.0 Hz, 4H; HC1 ), 7.16
8.4 Hz, J(H,P) ˆ 2.3 Hz, 2H; HC4 ), 6.53 (d, J(H,P) ˆ 1.6 Hz, 2H; HC4 ),
2
4
(dd, 3J(H,H) ˆ 8.6 Hz, 4J(H,P) ˆ 1.7 Hz, 4H; HC2 ), 7.28 7.56 (m, 22H;
6.58 (brd, 3J(H,H) ˆ 8.0 Hz, 2H; HC4 ), 6.98 (t, 3J(H,H) ˆ 8.1 Hz, 2H;
3
4
5
5
2
2
2
Harom), 7.66 (ttd, J(H,H) ˆ 7.1 Hz, J(H,H) ˆ 1.5 Hz, J(H,P) ˆ 1.7 Hz, 3H,
HC4 ), 7.05 7.20 (m, 12H; HC1 , HC2 , HC3 ), 7.35 7.63 (m, 29H; Harom),
3
3
HCP), 7.84 (d, 3J(H,H) ˆ 8.6 Hz, 4H, HC2 ), 7.93 ppm (dd, 3J(H,H) ˆ 7.6 Hz,
7.68 (d, 3J(H,H) ˆ 8.9 Hz, 4H; HC3 ), 7.95 (dd, 3J(H,H) ˆ 8.1 Hz, 4J(H,H) ˆ
6
6
4J(H,H) ˆ 1.4 Hz, 4 H, HC2 ); 13C{1H} NMR (CDCl3): d ˆ 13.6 (d, 2J(C,P) ˆ
1.6 Hz, 4H; HC2 ), 9.79 ppm (s, 2H; CHO); 13C{1H} NMR (CDCl3): d ˆ
4
2
2
4
5.5 Hz, S-CH3), 110.1 (s, C1 ), 117.5 (s, CN), 121.0 (d, 3J(C,P) ˆ 5.0 Hz, C2 ),
40.8 (s, NMe2), 106.4 (d, 3J(C,P) ˆ 5.7 Hz, C4 ), 108.6 (s, C4 ), 109.2 (d,
2
6
3
4
3
6
121.4 (d, 3J(C,P) ˆ 5.8 Hz, C1 ), 123.1 (s, C2 ), 124.7 (s, C2 ), 125.7 (dd,
5J(C,P) ˆ 1.1 Hz, C1 ), 109.9 (d, J(C,P) ˆ 4.9 Hz, C4 ), 117.8 (s, CN), 121.8
3
7
3
2
2
2
6
3
1J(C,P) ˆ 108.1 Hz, J(C,P) ˆ 4.3 Hz, Ci), 129.3 (s, C2 ), 129.6 (d, J(C,P) ˆ
(m, C2 , C1 ), 122.2 (d, 3J(C,P) ˆ 5.3 Hz, C3 ), 123.3 (s, C2 ), 124.4 (s, C2 ),
8
1
3
5
13.8 Hz, Cm), 131.8 (s, C2 ), 132.1 (d, 2J(C,P) ˆ 11.8 Hz, Co), 133.8 (s, CP),
127.5 (dd, J(C,P) ˆ 111.9 Hz, J(C,P) ˆ 4.1 Hz, Ci), 129.5 (s, C4 ), 129.6 (d,
7 3 8
134.4 (s, C1 ), 150.6 (d, 2J(C,P) ˆ 11.1 Hz, C2 ), 150.7 (s, C2 ), 152.2 (s, C2 ),
3J(C,P) ˆ 13.2 Hz, Cm), 129.6 (s, C2 ), 131.4 (s, C3 ), 131.6 (s, C2 ), 132.7 (d,
3
1
4
5
152.9 ppm (d, 2J(C,P) ˆ 9.8 Hz, C1 ), (CF3SO3À not detected); 19F{1H} NMR
2J(C,P) ˆ 11.4 Hz, Co), 132.8 (s, C3 ), 133.8 (d, J(C,P) ˆ 2.8 Hz, CP), 134.3
1
4
4
Chem. Eur. J. 2003, 9, 2151 2159
www.chemeurj.org
¹ 2003 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
2157

A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
(s, C1 ), 149.8 (brs, C2 ), 151.8 (s, C4 ), 152.9 (s, C2 ), 153.4 (d, 2J(C,P) ˆ
131.5 (s, C2 ), 131.8 (d, J(C,P) ˆ 10.5 Hz, C'o), 132.7 (d, J(C,P) ˆ 11.3 Hz,
3
4
3
5
8
2
2
1
1
5
3
8.9 Hz, C4 ), 153.6 (d, 2J(C,P) ˆ 9.2 Hz, C2 ), 154.4 (d, 2J(C,P) ˆ 9.3 Hz,
Co), 132.9 (brs, C'p), 133.7 (brs, CP), 134.1 (s, C3 ), 134.2 (s, C1 ), 140.5 (d,
1
1
3
4
4
C1 ), 156.7 (d, 2J(C,P) ˆ 8.5 Hz, C3 ), 191.3 ppm (s, CHO); IR (KBr): nÄ ˆ
1702 (CHO), 2228 cmÀ1 (CN); elemental analysis calcd (%) for
C86H71N12O10P5S (1619.5): C 63.78, H 4.42, N 10.38; found: C 63.66, H
4.37, N 10.25.
J(C,P) ˆ 13.8 Hz, C5 -CH N), 149.6 (brs, C2 ), 151.5 (d, 2J(C,P) ˆ 8.6Hz,
ˆ
C3 ), 151.7 (s, C4 ), 152.9 (s, C2 ), 153.4 (brd, 2J(C,P) ˆ 6.8 Hz, C6 ), 153.7 (d,
1
3
5
1
1
1
2J(C,P) ˆ 9.1 Hz, C5 ), 153.7 (d, 2J(C,P) ˆ 9.0 Hz, C2 ), 153.8 (d, 2J(C,P) ˆ
9.1 Hz, C4 ), 154.5 ppm (d, 2J(C,P) ˆ 9.4 Hz, C1 ), (C6 not detected);
19F{1H} NMR (CDCl3): d ˆ 13.9 (s, CF3); IR (KBr): nÄ ˆ 2225 cmÀ1 (CN);
elemental analysis calcd (%) for C204H169F24N26O20P13S7 (4387.8): C 55.84, H
3.88, N 8.30; found: C 55.76, H 3.82, N 8.22.
1
1
4
Dendron 6-G1: Trifluoro-p-cresol, sodium salt (0.192 g, 1.18 mmol) was
added to a solution of dendron 5-G1 (0.246 g, 0.288 mmol) in THF (10 mL).
The resultingmixture was stirred for 12 h at room temperature, centri-
fuged, and then evaporated to dryness. The residue was washed three times
with THF/pentane (1/5) to afford 6-G1 as a pale yellow powder in 93%
yield. 1H NMR (CDCl3): d ˆ 3.39 (d, 3J(H,P) ˆ 11.1 Hz, 6H; P6-N-CH3),
6.15 (ddd, 3J(H,P) ˆ 24.0 Hz, 3J(H,H)a ˆ 18.3 Hz, 2J(H,H) ˆ 1.2 Hz, 1H;
Hc), 6.40 (ddd, 3J(H,P) ˆ 45.9 Hz, 3J(H,H)a ˆ 12.5 Hz, 2J(H,H) ˆ 1.2 Hz,
1H; Hb), 6.87 (dddd, 2J(H,P) ˆ 30.6 Hz, 3J(H,H)c ˆ 18.3 Hz, 3J(H,H)b ˆ
12.5 Hz, 4J(H,P) ˆ 1.2 Hz, 1H; Ha), 7.29 (dd, 3J(H,H) ˆ 8.7 Hz, 4J(H,P) ˆ
X-ray structure analysis: Data collection was performed at low temper-
ature (Tˆ 160 K) for 2-(PN)1 and (Tˆ 180 K) for 3-(PN)1 on a Stoe
Imaging Plate Diffraction System (IPDS), equipped with an Oxford
Cryosystems Cryostream Cooler Device and graphite-monochromated
MoKa radiation (l ˆ 0.71073 ä). Standard reflections were monitored
periodically; they showed no change during data collection, corrections
were made for Lorentz and polarization effects. Absorption corrections
2
2
1.8 Hz, 4H; HC5 ), 7.36 (brd, 3J(H,H) ˆ 8.4 Hz, 8H; HC6 ), 7.48 (™t∫d,
]
(Difabs)[17 were applied. Structures were solved by direct methods with
3J(H,H) ˆ 7.8 Hz, 4J(H,P) ˆ 3.3 Hz, 4H; HC'm), 7.54 7.65 (m, 8H, HC'p,
SIR92,[18] and some difference Fourier maps techniques, then refined by
least-squares procedures on a F 2 with SHELXL97.[19] All hydrogen atoms
were located on a difference Fourier maps and refined with a ridingmodel
and isotropic thermal parameters fixed at 20% higher than those of the
carbon atoms to which they are connected. For both structures all non-
hydrogen atoms were anisotropically refined, and weighting schemes were
applied in the last cycles of refinement; the weights were calculated with
HC53; CH ˆ N), 7.62 (brd, 3J(H,H) ˆ 8.4 Hz, 8H; HC6 ), 7.68 ppm (ddd,
3
4
3
3J(H,H) ˆ 6.9 Hz, J(H,H) ˆ 1.5 Hz, J(H,P) ˆ 13.2 Hz, 4H; HC'o); 13C{1H}
NMR (CDCl3): d ˆ 32.8 (d, 2J(C,P) ˆ 13.5 Hz, P6-N-CH3), 121.7 (d,
2
2
3J(C,P) ˆ 4.8 Hz, C6 ), 121.9 (d, 3J(C,P) ˆ 5.7 Hz, C5 ), 123.6 (q, 1J(C,F) ˆ
3
271.8 Hz, CF3), 126.8 (brq, 3J(C,F) ˆ 3.2 Hz, C6 ), 127.4 (d, 1J(C,P) ˆ
4
3
97.4 Hz, CHa), 127.5 (q, 2J(C,F) ˆ 33.0 Hz, C6 ), 127.9 (s, C5 ), 128.6 (d,
4
3J(C,P) ˆ 13.2 Hz, C'm), 128.8 (part of doublet of C'i), 130.4 (s, C5 ), 132.0 (d,
the followingformula: w ˆ 1/[s2(Fo2† ‡ (aP)2 ‡ bP], where P ˆ (Fo2
‡
3
2J(C,P) ˆ 11.4 Hz, C'o), 132.6 (s, C'p), 136.7 (s, CH2 ˆ ), 139.9 (d, J(C,P) ˆ
2Fc2†/3. The molecules were drawn with the program ORTEP32[20] with
4
1
13.8 Hz, C5 -CH ˆ N), 152.8 (d, 2J(C,P) ˆ 6.7 Hz, C6 ), 153.2 ppm (d,
50% probability displacement ellipsoids for non-hydrogen atoms.
1
2J(C,P) ˆ 8.8 Hz, C5 ); 19F{1H} NMR (CDCl3): d ˆ 13.9 ppm (s, CF3);
elemental analysis calcd (%) for C58H45F12N5O6P4S3 (1356.1): C 51.37, H
3.34, N 5.16; found: C 51.25, H 3.27, N 5.03.
[1] a) I. Manners, Angew. Chem. 1996, 108, 1712; Angew. Chem. Int. Ed.
Engl. 1996, 35, 1602; b) A. R. Mc Williams, H. Dorn, I. Manners, Top.
Curr. Chem., 2001, 220, 141.
[2] a) R. Schwesinger, H. Schlemper, Angew. Chem. 1987, 99, 1212;
Angew. Chem. Int. Ed. Engl. 1987, 26, 1167; b) R. Schwesinger, C.
Hasenfratz, H. Schlemper, L. Walz, E. M. Peters, K. Peters, H. G.
von Schnering, Angew. Chem. 1993, 105, 1420; Angew. Chem. Int. Ed.
Engl. 1993, 32, 1361.
[3] J. E. Mark, H. R. Allcock, R. West, Inorganic Polymers, Prentice Hall,
Englewood Cliffs, New Jersey, 1992.
[4] a) H. R. Allcock, Angew. Chem. 1977, 89, 153; Angew. Chem. Int. Ed.
Engl. 1977, 16, 147; b) R. H. Neilson, P. Wisian-Neilson, Chem. Rev.
1988, 88, 541; c) H. R. Allcock, Appl. Organomet. Chem. 1998, 12,
659.
Compound 7-G1: MeNHNH2 (30 equiv, 173 mL, 3.25 mmol) was added to a
solution of 6-G1 (0.147 g, 0.108 mmol) in THF (10 mL). The resulting
mixture was stirred for 2 h at room temperature and then evaporated to
dryness. The residue was washed with THF/pentane (1/5) to afford 7-G1 as
1
a white powder in 96% yield. H NMR (CDCl3): d ˆ 2.38 (s, 3H; CH3-N-
NH2), 2.65 (m, 2H; CH2-CH2-P5), 2.82 (brs, 2H; NH2), 3.08 (m, 2H; CH2-
P5), 3.40 (d, 3J(H,P) ˆ 10.8 Hz, 6H; P6-N-CH3), 7.30 (dd, 3J(H,H) ˆ 8.7 Hz,
2
3
2
4J(H,P) ˆ 1.5 Hz, 4H; HC5 ), 7.37 (brd, J(H,H) ˆ 8.4 Hz, 8H; HC6 ), 7.47
(™t∫d, 3J(H,H) ˆ 7.5 Hz, 4J(H,P) ˆ 3.3 Hz, 4H; HC'm), 7.52 7.68 (m, 8H,
3
3
HC'p, HC5 ; CH N), 7.62 (brd, 3J(H,H) ˆ 8.4 Hz, 8H; HC6 ), 7.74 ppm
(ddd, 3J(H,H) ˆ 6.9 Hz, 4J(H,H) ˆ 1.5 Hz, 3J(H,P) ˆ 12.9 Hz, 4H; HC'o);
13C{1H} NMR (CDCl3): d ˆ 25.8 (d, 1J(C,P) ˆ 66.4 Hz, CH2-P5), 33.4 (d,
2J(C,P) ˆ 13.6 Hz, P6-N-CH3), 50.9 (s, CH3-N-NH2), 54.9 (s, CH2-CH2-P5),
ˆ
2
2
122.3 (d, 3J(C,P) ˆ 4.8 Hz, C6 ), 122.6 (d, 3J(C,P) ˆ 5.1 Hz, C5 ), 124.2 (q,
[5] H. W. Roesky, W. Grosse Bˆwing, E. Niecke, Chem. Ber. 1971, 104,
653.
[6] a) J. M. J. Frechet, Science, 1994, 263, 1710; b) J. C. M. van Hest,
1J(C,F) ˆ 272.0 Hz, CF3), 127.4 (brq, 3J(C,F) ˆ 3.2 Hz, C6 ), 128.4 (s, C5 ),
129.2 (d, 3J(C,P) ˆ 13.5 Hz, C'm), 129.4 (dd, 1J(C,P) ˆ 105.8 Hz, 3J(C,P) ˆ
3
3
¬
4
5.8 Hz, C'i), 131.0 (s, C5 ), 131.8 (d, 2J(C,P) ˆ 10.5 Hz, C'o), 132.9 (d,
D. A. P. Delnoye, M. W. P. L. Baars, M. H. P. van Genderen, E. W.
Meijer, Science, 1995, 268, 1592; c) M. R. Leduc, C. J. Hawker, J. Dao,
J. M. J. Frechet, J. Am. Chem. Soc. 1996, 118, 11111.
3
4
4J(C,P) ˆ 2.7 Hz, C'p), 140.5 (d, J(C,P) ˆ 13.7 Hz, C5 -CH N), 153.4 (d,
ˆ
1
1
4
2J(C,P) ˆ 6.1 Hz, C6 ), 153.7 ppm (d, 2J(C,P) ˆ 9.0 Hz, C5 ), (C6 not
detected); 19F{1H} NMR (CDCl3): d ˆ 13.9 ppm (s, CF3); elemental analysis
calcd (%) for C59H51F12N7O6P4S3 (1402.2): C 50.54, H 3.67, N 6.99; found: C
50.48, H 3.59, N 7.03.
¬
¬
[7] I. Gitsov, K. L. Wooley, J. M. J. Frechet, Angew. Chem. 1992, 104,
1282; Angew. Chem. Int. Ed. Engl. 1992, 31, 1200.
[8] For a review, see: A. D. Schl¸ter, J. P. Rabe, Angew. Chem. 2000, 112,
860; Angew. Chem. Int. Ed. 2000, 39, 864.
Compound 8-G2: A solution of 7-G1 (0.0213 mg, 15.2 mmol) in THF (5 mL)
was added at room temperature to a solution of 2-(PN)4 (0.0123 g, 7.6 mmol)
in THF (5 mL). The solution was stirred for 12 h, and then evaporated to
dryness. The residue was washed three times with THF/pentane (1/20), to
afford 8-G2 as an orange powder in 95% yield. 1H NMR (CDCl3): d ˆ 2.69
(s, 6H; CH3-N-CH2-CH2-P5), 2.72 (s, 12H; NMe2), 3.07 (m, 4H; CH2-CH2-
P5), 3.37 (d, 3J(H,P) ˆ 10.8 Hz, 12H; P6-N-CH3), 3.60 (m, 4H; CH2-P5), 6.34
¬
[9] a) C. Larre, A. M. Caminade, J. P. Majoral, Angew. Chem. 1997, 109,
¬
614; Angew. Chem. Int. Ed. Engl. 1997, 36, 596; b) C. Galliot, C. Larre,
A. M. Caminade, J. P. Majoral, Science 1997, 277, 1981; c) C. Larre, B.
Donnadieu, A. M. Caminade, J. P. Majoral, J. Am. Chem. Soc. 1998,
120, 4029; d) C. Larre, D. Bressolles, C. Turrin, B. Donnadieu, A. M.
Caminade, J. P. Majoral, J. Am. Chem. Soc. 1998, 120, 13070; e) J. P.
Majoral, C. Larre, R. Laurent, A. M. Caminade, Coord. Chem. Rev.
1999, 190 192, 3.
¬
¬
6
(dd, 3J(H,H) ˆ 8.4 Hz, 4J(H,P) ˆ 2.4 Hz, 2H; HC4 ), 6.55 6.62 (m, 4H;
¬
2
4
HC4 , HC4 ), 6.80 7.92 ppm (m, 125H; Harom, CH N); 13C{1H} NMR
(CDCl3): d ˆ 24.8 (d, 1J(C,P) ˆ 63.5 Hz, CH2-P5), 33.4 (d, 2J(C,P) ˆ 13.4 Hz,
P6-N-CH3), 38.1 (s, CH3-N-CH2-CH2-P5), 40.8 (s, NMe2), 52.0 (s, CH2-CH2-
ˆ
[10] CCDC-196947 (2-(PN)1) and CCDC-196948 (3-(PN)1) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB21EZ, UK; fax: (‡44)1223-336033; or depos-
it@ccdc.cam.uk).
[11] Startingfrom this step, all the experiments must be carried out in the
dark on account of the facile isomerization (E ! Z) of the azobenzene
linkage: R. M. Sebastian, J. C. Blais, A. M. Caminade, J. P. Majoral,
Chem. Eur. J. 2002, 8, 2172.
2
4
4
P5), 106.6 (d, 3J(C,P) ˆ 5.7 Hz, C4 ), 108.4 (s, C4 ), 108.9 (s, C1 ), 110.2 (d,
6
3
2
3J(C,P) ˆ 4.9 Hz, C4 ), 118.6 (s, CN), 121.5 (d, J(C,P) ˆ 5.0 Hz, C2 ), 121.8
2
2
2
(d, 3J(C,P) ˆ 5.0 Hz, C1 ), 122.3 (d, 3J(C,P) ˆ 4.8 Hz, C3 , C6 ), 122.4 (d,
2
6
3
3J(C,P) ˆ 4.7 Hz, C5 ), 123.2 (s, C2 ), 124.4 (s, C2 ), 124.4 (q, 1J(C,F) ˆ
3
3
3
272.0 Hz, CF3), 126.7 (s, C3 ), 127.4 (brq, J(C,F) ˆ 2.8 Hz, C6 ), 127.9 (dd,
3
3
3
1J(C,P) ˆ 109.2 Hz, J(C,P) ˆ 3.9 Hz, Ci), 128.4 (s, C5 ), 129.2 (d, J(C,P) ˆ
12.7 Hz, C'm), 129.3 (dd, 1J(C,P) ˆ 107.3 Hz, 3J(C,P) ˆ 5.3 Hz, C'i), 129.4 (s,
5
7
4
4
C4 ), 129.5 (s, C2 ), 129.5 (d, 3J(C,P) ˆ 13.1 Hz, Cm), 131.1 (brs, C3 , C5 ),
2158
¹ 2003 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2003, 9, 2151 2159

Multifunctional Linear Multiphosphazenes
2151 2159
[12] H. Sun, J. Am. Chem. Soc. 1997, 119, 3611.
[13] H. R. Allcock, Chem. Rev. 1972, 72, 315.
[14] a) E. Fluck, Z. Anorg. Allg. Chem. 1962, 315, 191; b) H. R. Allcock,
N. M. Tollefson, R. A. Arcus, R. R. Whittle, J. Am. Chem. Soc. 1985,
107, 5166.
[17] N. Walker, D. Stuart, DIFABS Acta Crystallogr., Sect A 1983, 39, 158.
[18] A. Altomare, G. Cascarano, G. Giacovazzo, A. Guagliardi, M. C.
Burla, G. Polidori, M. Camalli, SIR92 program for automatic solution
of crystal structures by direct methods. J. Appl. Crystallogr. 1994, 27,
435.
[15] a) V. Maraval, R. Laurent, B. Donnadieu, M. Mauzac, A. M.
Caminade, J. P. Majoral, J. Am Chem. Soc. 2000, 122, 2499; b) V.
Maraval, R. Laurent, S. Merino, A. M. Caminade, J. P. Majoral, Eur. J.
Org. Chem. 2000, 3555.
[19] G. M. Sheldrick, (1997) SHELXL97. Program for the refinement of
Crystal Structures. University of Gˆttingen (Germany).
[20] L. J. Farrugia, ORTEP3 for Windows J. Appl. Crystallogr. 1997, 30,
565.
[16] J. Mitjaville, A. M. Caminade, J. C. Daran, B. Donnadieu, J. P.
Majoral, J. Am. Chem. Soc. 1995, 117, 1712.
Received: December 3, 2002 [F4630]
Chem. Eur. J. 2003, 9, 2151 2159
www.chemeurj.org
¹ 2003 Wiley-VCH VerlagGmbH & Co. KGaA, Weinheim
2159