Chemistry of diphenyltetrafluorophosphazene: Reactions with dilithiated diols

Article abstract of DOI:10.1016/j.jfluchem.2006.05.001

Reaction of gem-diphenyltetrafluorophosphazene, [1,1-(C₆H₅)₂]P₃N₃F₄ (1) with LiO(CH₂)₃OLi resulted in the formation of four products, spiro-{3,3-[O(CH₂)

Full text of DOI:10.1016/j.jfluchem.2006.05.001

Journal of Fluorine Chemistry 127 (2006) 1046–1053
www.elsevier.com/locate/fluor
Chemistry of diphenyltetrafluorophosphazene:
Reactions with dilithiated diols
a
a
b
Anil J. Elias a, , K. Muralidharan , M. Senthil Kumar , P. Venugopalan
*
a Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110 016, India
b Department of Chemistry, Panjab University, Chandigarh, Punjab, India
Received 22 March 2006; received in revised form 27 April 2006; accepted 2 May 2006
Available online 6 May 2006
Abstract
Reaction of gem-diphenyltetrafluorophosphazene, [1,1-(C6H5)2]P3N3F4 (1) with LiO(CH2)3OLi resulted in the formation of four products, spiro-
{3,3-[O(CH2)3O]}[1,1-(C6H5)2]P3N3F2 (2), ansa-{3,5-[O(CH2)3O]}[1,1-(C6H5)2P3N3F2] (3), bridged-[1,1-(C6H5)2N3P3F3][O(CH2)3O][1,1-
(C6H5)2N3P3F3] (4) and dangling-[HO(CH2)3O][1,1-(C6H5)2P3N3F3] (5) derivatives of 1, among which compound 5 was found to be the major
product. Reaction of 1 with the dilithiated ferrocene derived diol, FcCH2P(S)(CH2OLi)2 resulted in the formation of two isomers of ansa substituted
fluorophosphazenes namely endo-[1,1-(C6H5)2]{3,5-[FcCH2P(S)(CH2O)2]}P3N3F2 (6) and exo-[1,1-(C6H5)2]{3,5-[FcCH2P(S)(CH2O)2]}P3N3F2
(7). These were formed along with the spiro isomer [1,1-(C6H5)2]{3,3-[FcCH2P(S)(CH2O)2]}P3N3F2 (8) the dangling derivative [1,1-
(C6H5)2P3N3F3][OCH2(FcCH2)P(S)CH2OH] (9) and the bridged compound [1,1-(C6H5)2P3N3F3][OCH2(FcCH2)P(S)CH2O][1,1-(C6H5)2P3N3F3]
(10). All compounds were separated by column chromatography and characterized by 1H, 31P{1H}, 19F NMR, mass spectra and elemental analysis.
The spirocyclic compound 8 was also characterized by X-ray crystallography.
# 2006 Elsevier B.V. All rights reserved.
Keywords: gem-Diphenyltetrafluorophosphazene; Spiro; Ansa; Bridged; Dangling; Dilithiated diols
1. Introduction
have been reported so far [8]. The replacement of geminal
fluorines on the fluorophosphazene trimer by phenyl groups can
be expected to have steric as well as electronic effects on the
nature of products formed in the substitution reactions of this
phosphazene with bifunctional reagents.
Monoaryl and geminal diaryl substituted trimeric fluoropho-
sphazenes are an interesting class of compounds, which unlike
N3P3F6, are easy to handle due to their lesser volatility [1]. A
few of them have been reported as potential precursors for
realizing high molecular weight phosphazene polymers [2]. A
scan of the literature shows that unlike the reactions of the aryl
and gem-diaryl chlorophosphazenes, the reactions of aryl
substituted fluorophosphazenes have been little explored [3–5].
Quite interestingly, detailed studies on the reactions of gem-
diphenyltetrachlorophosphazene, [1,1-(C6H5)2]P3N3Cl4 with a
variety of short chain diols and amino alcohols yielded only
spirocyclic products [6,7]. It is interesting to note that except
for a report of a reaction of gem-diphenyltetrafluoropho-
sphazene with dilithiated ferrocene, no other reactions of
bifunctional reagents with aryl substituted fluorophosphazenes
The reactions of dilithiated diol FcCH2P(S)(CH2OLi)2 with
N3P3F6 and N3P3Cl6 as well as the reactions of LiO(CH2)3OLi
with N4P4F8 at ꢀ80 8C was found to yield the corresponding
ansa substituted products [9–11]. We have also shown that
lithiated diols react quite differently with fluorophosphazenes
when compared to silylated diols with the former forming
preferentially the kinetically controlled ansa substituted
products [9]. Comparison of reactions of disodium and
dilithium salts of a diol with N3P3Cl6 also shows interesting
differences in the nature and yield of cyclized products [12]. In
this context, we were interested in exploring the reactions of
gem-diphenyltetrafluorophosphazene, [1,1-(C6H5)2]P3N3F4 (1)
with difunctional reagents, especially with dilithiated diols. In
this paper we describe the first systematic study on the
chemistry of gem-diphenyltetrafluorophosphazene with two
different dilithiated diols FcCH2P(S)(CH2OLi)2 and LiO
* Corresponding author. Tel.: +91 11 26591504; fax: +91 11 26581102.
E-mail address: eliasanil@gmail.com (A.J. Elias).
0022-1139/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2006.05.001

A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
1047
Scheme 1.
(CH2)3OLi. We also describe the preparation of the tetra-
fluorinated phosphazene (1) by an alternate and easier synthetic
route, which does not involve the use of volatile N3P3F6.
1, based on N3P3Cl6. The present method, which involves
Friedel–Craft’s arylation of N3P3Cl6, followed by fluorination
of the tetrachloro compound by KF/CH3CN, reduces one step in
comparison to the reported procedure, and does not involve
handling of the volatile N3P3F6, resulting in a good yield of 1.
To explore the effect of the presence of two geminal phenyl
groups on the fluorophosphazene on its reactions with
bifunctional reagents, we have carried out reaction of
dilithiated propanediol LiO(CH2)3OLi with 1. The reaction
resulted in the formation of four products, viz. spiro-{3,3-
[O(CH2)3O]}[1,1-(C6H5)2]P3N3F2 (2), ansa-{3,5-[O(CH2)3O]}
[1,1-(C6H5)2]P3N3F2 (3), bridged-[N3P3F3(C6H5)2][O(CH2)
3O] [N3P3F3(C6H5)2] (4) and dangling-[HO(CH2)3O](C6H5)
2P3N3F3 (5) derivatives of gem-diphenyltetrafluorophospha-
2. Results and discussion
The
gem-diphenyltetrafluorophosphazene,
[1,1-
(C6H5)2]P3N3F4 (1) was prepared from N3P3Cl6 as shown in
Scheme 1 Compound 1 was prepared earlier by a three-step
procedure starting from chlorophosphazene trimer, which
involved fluorination of N3P3Cl6 to N3P3F6, reaction of N3P3F6
with phenyllithium to yield N3P3F5(C6H5) followed by Friedel–
Crafts arylation of N3P3F5(C6H5) [13]. This method involved
loss of compounds in each step resulting in a moderate yield of
Scheme 2.
Scheme 3.

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A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
(CH2)3OH when reacted with compound 1 yielded the dangling
derivative 5 in 70% yield. In this reaction, compound 1 was
added to the monolithiated diol at ꢀ80 8C and the reaction was
allowed to reach room temperature within 2 h. Then the mixture
was stirred for 12 h at room temperature followed by reflux at
65 8C. This is one of the highest yields of dangling derivative of
phosphazenes obtained in a reaction of cyclophosphazene with
bifunctional reagents.
The reaction of the dilithiated diol, FcCH2P(S)(CH2OLi)2
with the gem-diphenylfluorophosphazene (1) resulted in the
formationoftwoansasubstitutedfluorophosphazenesendo-[1,1-
(C6H5)2]{3,5-[FcCH2P(S)(CH2O)2]}P3N3F2 (6) and exo-[1,1-
(C6H5)2]{3,5-[FcCH2P(S)(CH2O)2]}P3N3F2 (7) along with their
spiro isomer [1,1-(C6H5)2]{3,3-[FcCH2P(S)(CH2O)2]}P3N3F2
(8) (Scheme 3).
This reaction also yielded the dangling (C6H5)2P3N3F3
[OCH2(FcCH2)P(S)CH2OH] (9) and bridged [(C6H5)2P3N3F3]
[OCH2(FcCH2)P(S)CH2O][(C6H5)2P3N3F3] (10) derivatives of
1. All the products were separated by column chromatography
and were characterized by 31P{1H}, 19F NMR and mass spectra
and elemental analysis. The spirocyclic compound 8 was also
characterized by X-ray crystallography. Similar to the reaction
of LiO(CH2)3OLi, the major product from the reactions of
FcCH2P(S)(CH2OLi)2 with 1 was the dangling derivative.
These results differ significantly from the reactions of the same
dilithiated diol with N3P3F6 where under similar conditions
ansa substituted compounds were found to be the major
products [9].
Fig. 1. 31P{1H} NMR spectra of (a) bridged 4, (b) ansa 3, (c) spiro 2 and (d)
dangling 5 derivatives of 1,1-(C6H5)2P3N3F4 with 1,3-propanediol.
zene (Scheme 2). All these products were separated by column
chromatography over silica gel and were characterized by
1
31P{1H}, 19F and H NMR spectroscopic analysis.
Albeit this reaction yielded four possible products that are
obtainable from a reaction of bifunctional reagents with
cyclophosphazene trimer, the dangling derivative was obtained
in higher yields when compared to the other products isolated
from this reaction. Recent interest on the usefulness of
exploring the chemistry of cyclic phosphazenes has been
centered not only on their usefulness as precursors for
phosphazene based polymers [14,15], but also in the use of
the trimeric and tetrameric phosphazene as a stable core for the
synthesis of dendrimers both by the convergent and divergent
synthesis [16,17]. The dangling phosphazene derivatives are
potential precursors for realizing phosphazene based dendri-
mers by convergent synthesis.
2.1. Spectral studies on the gem-
diphenylfluorophosphazene and its derivatives with diols
The 31P{1H} spectra of compounds 2–5 are shown in Fig. 1.
The PF2 groups are clearly identifiable by the triplet of
1
multiplets with JPF around 900 Hz. In the case of the
spirocyclic compound 2, the phosphorus signal due to P(OR)2
moiety has merged with the signal of the PF2 triplet. Among the
PF(OR) signals which appeared as doublet multiplets, the
signal for the ansa compound 3 is found to be relatively more
deshielded. The 31P{1H} NMR spectral data of compounds 2–
10 along with 1 are given in Table 1. It is clear from the table
that for all the compounds, the chemical shifts of phosphorus
atoms bound to the diols are more deshielded as the electro
negativity of the substituent group on the phosphorus has
increased. It can be seen from Table 1 that as we move from PF2
The conversion of the lithium alkoxy terminated dangling
derivative to the hydroxy terminated dangling derivative
possibly took place while working up the reaction by
chromatography over silicagel. To cross check the propensity
of this reaction for formation of higher yields of the dangling
derivative, we have carried out reaction of 1 with monolithiated
1,3-propanediol. LiO(CH2)3OH, which was prepared in situ by
controlled lithiation of 1,3-propanediol using n-BuLi. LiO

A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
1049
Table 1
31P{1H} NMR spectral data of compound 1 and its derivatives with bifunctional reagents
Compound
31P{1H} NMR (d in ppm)
PF2 (1JPF, Hz)
OPF (1JPF, Hz)
OPO (2JPNP, Hz)
P(C6H5)2 (2JPNP, Hz)
1
2
3
4
5
6
7
8
9
mt, 7.6 (911)
mt, 6.78 (906)
–
–
–
t, 25.83 (49)
t, 23.94 (43)
tt, 26.88 (42)
t, 24.70 (44)
t, 24.70 (43)
t, 25.41 (44)
t, 26.81 (40)
t, 24.54 (45)
m, 25.01
–
m, 11.78
md, 18.06 (910)
md, 12.77 (884)
md, 12.74 (895)
dd, 14.76 (955)
dd, 12.28 (921)
–
–
md, 7.88 (902)
mt, 7.88 (902)
–
–
–
–
–
–
ddt, 4.95 (905)
mt, 7.58 (933)
mt, 7.45 (905)
ddt, 13.65 (56.1)
md, 13.39 (921)
md, 13.09 (916)
–
–
10
t, 25.25 (44)
to PPh2, the corresponding chemical shifts are deshielded more
for the groups PF2, OPF, OPO and P(C6H5)2, respectively. It can
also be observed that the P(C6H5)2 chemical shifts are not much
altered in the 31P{1H} NMR spectra of the compounds 2–10
compared to that of the starting compound 1.
the spiro compound 8 it was observed at 19.19 ppm. Similar
observations were noted for the eight and six membered ring
compounds formed by FcCH2P(S)(CH2OH)2 with other chloro
and fluorophosphazenes [9,18]. As observed for the compounds
3 and 5, the 31P{1H} and 19F NMR spectra of dangling and
bridged compounds, 9 and 10 were also identical. In the 31P
NMR spectra, the P S peak appeared at 40.10 and 40.28 ppm,
respectively for the compounds 9 and 10. The presence of
different signals for the CH2OP and CH2OH groups as well as
the signal for OH group in the 1H NMR confirmed the identity
of the dangling compound 9. Molecular ions peaks were
obtained for all the new compounds in their mass spectra
recorded in the FAB mode.
A clear difference in the mobility while doing column
chromatography over silica gel made it easy to separate the
bridged and dangling derivatives, 4 and 5. The 31P{1H} and 19
F
NMR spectra of these two compounds are as expected,
identical. But, they differ in 1H and 13C{1H} NMR spectra. In
1
the H NMR spectra of the bridged compound 4, two sets of
peaks for aliphatic groups are observed, while for the dangling
derivative 5, three sets of peaks are observed for the same.
Apart from this, for the dangling derivative 5, a broad peak
corresponding to the OH group at 2.41 ppm is also observed. In
the IR spectra of the compound 5, a broad –OH stretching
frequency at 3419 cmꢀ1 is observed, which is not observed for
the compound 4. The identity of these compounds is also
confirmed by mass spectroscopy and elemental analysis.
In the 31P{1H} NMR spectra of the compounds 6–10, the
P S chemical shift of the ansa substituted compounds 6 and 7
were observed at 45.13 and 47.55 ppm, respectively, while for
2.2. Crystal structure of spiro substituted compound 8
The X-ray crystal structure of the spiro substituted
compound [1,1-(C6H5)2]{3,3-[FcCH2P(S)(CH2O)2]}P3N3F2
(8) is given in Fig. 2. The details pertaining to data collection
and structure solution for compound 8 are summarized in
Table 2. The selected bond lengths and bond angles are given in
Table 3.
Fig. 2. Crystal structure of the spirocyclic compound 8.

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A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
Table 2
Table 3
Selected bond lengths (A) and bond angles (8) for the compound 8
˚
X-ray crystallographic parameters for 8
Formula
Fw
C25H25F2FeN3O2P4S
649.25
Bond lengths
P3–N1
1.607(3)
1.798(3)
1.560(3)
1.583(2)
1.561(3)
1.530(2)
1.825(3)
1.816(3)
P3–N2
P3–C2
P2–N3
P2–O2
P4–N2
P4–F2
P1–C13
P1–S1
1.609(3)
1.790(3)
1.588(3)
1.594(2)
1.550(3)
1.533(2)
1.817(3)
1.9359(12)
Cryst syst
Monoclinic
C2/c
P3–C14
P2–N1
P2–O1
P4–N3
P4–F1
Space group
˚
a (A)
˚
b (A)
28.932(3)
9.053(1)
23.677(2)
90
˚
c (A)
a (8)
b (8)
g (8)
P1–C12
P1–C11
112.21(1)
90
Bond angles
N2–P3–N1
N2–P4–N3
N3–P2–N1
C12–P1–C13
C13–P1–C11
P2–N1–P3
3
˚
V (A )
5741.4(1)
8
115.40(14)
119.78(14)
119.15(14)
101.01(15)
105.88(15)
121.06(16)
C20–P3–C14
F1–P4–F2
105.27(14)
96.72(12)
Z
rcalcd (g cmꢀ3
)
1.502
O1–P2–O2
C12–P1–C11
P4–N3–P2
N1–P3–N2
103.73(11)
102.47(16)
119.51(17)
115.40(14)
m (mmꢀ1
)
0.863
˚
l (A)
0.71073
293 (2)
T (8C)
R1, wR2 [I < 2s(I)]a
R1, wR2 (all data)a
GoF
0.0356, 0.0819
0.0595, 0.0897
1.023
P
P
P
P
2 1=2
a
R = jF0j ꢀ jFcj/ jFcj; wR2 ¼ ½wðF02 ꢀ Fc2Þꢁ= ½wðF02Þ ꢁ
.
the phosphazene ring (Fig. 3d). But in the case of the spiro
compound 8, the same phosphorus atom is deviated only to a
˚
distance of 0.0037 A from the mean plane defined by the
The crystal structure of the spirocyclic derivative of gem-
diphenylfluorophosphazene (8) shows that the phosphazene
ring is slightly puckered (Fig. 3b) from planarity in
comparison to N3P3F6 (Fig. 3a) [19,20]. It has been reported
that one of the phosphorus atoms that is bearing the phenyl
groups in the phosphazene ring of the gem-diphenyl
tetrafluorophosphazene was deviated to a distance of
other five atoms of the ring. But if the mean plane is defined
by the all the six atoms of the phosphazene ring, five of the
atoms are deviated significantly from the plane. This causes
puckering of the N3P3 ring (Fig. 3c). This kind of puckering
of the fluorophosphazenes ring, which was not observed for
the monospiro compound of fluorophosphazene [9], indicates
the possible electronic influence of geminal phenyl groups on
the planarity of the phosphazene ring.
˚
0.20 A from the plane defined by the other five atoms of
Fig. 3. The comparison of mean planes formed by phosphazene ring (a) of N3P3F6 [19], (b) of monospiro {1,1-[FcCH2P(S)(CH2O)2]}N3P3F4 [9], (c) of monospiro
[1,1-(C6H5)]{3,3-[FcCH2P(S)(CH2O)2]}N3P3F2 (8) and (d) of 1,1-(C6H5)2N3P3F4 [13].

A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
1051
3. Conclusions
4.3. Synthesis
The gem-diphenyltetrafluorophosphazene, [1,1-(C6H5)2]P3
N3F4 was prepared by an alternate method in good yields by
the fluorination of [1,1-(C6H5)2]P3N3Cl4 using KF/CH3CN. A
systematic study of its reactions with two dilithiated diols has
been carried out. Unlike [1,1-(C6H5)2]P3N3Cl4, which
yielded exclusively spiro substituted products with diols
and aminoalcohols, the reactions of the gem-diphenyltetra-
fluorophosphazene yielded all the possible products of such a
reaction namely the bridged, ansa, spiro and dangling
derivatives. The study indicates the usefulness of dilithiation
route for making ansa, bridged and dangling derivatives of the
diphenyl fluorophosphazene. The experiments differ signifi-
cantly when compared to similar reactions of N3P3F6 and
indicate that dangling derivative is the major product in these
reactions thus providing a good synthetic route for the
dangling derivatives of [1,1-(C6H5)2]P3N3F4. By doing the
reaction with monolithiated diols, the yields of dangling
derivatives has been increased further. Unlike the crystal
structure of [1,1-(C6H5)2]N3P3F4, wherein the phenyl bearing
P atom alone is found to be away from the mean plane of the
ring, or the crystal structure of monospirocyclic compound
{1,1-[FcCH2P(S)(CH2O)2]}N3P3F4 wherein the N3P3 ring is
planar, the phosphazene ring in compound 8 is found to be
puckered.
4.3.1. Preparation of gem-diphenyltetrachlorophosphazene
(1)
The compound [1,1-(C6H5)2]P3N3Cl4 [23] (3.26 g,
7.5 mmol) was dissolved in 50 mL of acetonitrile and
potassium fluoride (2.19 g, 37.7 mmol) was added to it. The
mixture was refluxed in acetonitrile for 10 h. Then the
acetonitrile was evaporated off and the residue was dissolved
in dichloromethane to filter off the KCl formed in the reaction.
The mixture was purified by column chromatography over
silica gel using a mixture of 2% dichloromethane in hexane as
eluent to get the pure gem-diphenyl tetrafluorophosphazene,
[1,1-(C6H5)2]P3N3F4 (1). Yield: 2.00 g, 72.4%; mp: 63 8C.
NMR: 31P{1H}, d 25.83 [t (2JPF = 49 Hz), P(C6H5)2], 7.6 [mt
(1JPF = 911 Hz), PF2]; 19F, d ꢀ67.57 [md (1JPF = 937 Hz), PF2].
4.3.2. Reaction of the LiO(CH2)3OLi with compound 1
The diol, HO(CH2)3OH (0.15 g, 2.0 mmol) was dilithiated
by reacting with n-BuLi (2.50 mL, 4.0 mmol) at ꢀ80 8C in
THF (20 mL). After 4 h of stirring, compound 1 (1.00 g,
2.7 mmol) dissolved in 20 mL of THF was added to the above
solution dropwise at ꢀ80 8C with constant stirring. The mixture
was allowed to reach room temperature over a period of 2 h, and
then stirred further for 12 h. Afterwards, the THF was
evaporated off and the mixture was dissolved in dichloro-
methane followed by filtration of LiF formed in the reaction.
The mixture was analyzed by TLC and 31P{1H} NMR
spectroscopy and the presence of four products were observed.
The products were separated by column chromatography over
silica gel using ethylacetate/hexane mixture as eluent. The first
compound which came out of the column, obtained as viscous
liquid was identified as the bridged-[N3P3F3(C6H5)2]O(-
4. Experimental
4.1. General experimental procedures
A conventional vacuum line equipped with a dry
nitrogen apparatus and Schlenk glassware was used for all
reactions. Reactions and work up procedures were carried
out under an atmosphere of dry nitrogen. N3P3F6 was
prepared from N3P3Cl6 (Fluka) according to the literature
method [21] and was purified by fractional distillation
(caution: N3P3F6 is a potentially toxic compound and
has high vapor pressure at room temperature). The synthesis
of the diol, FcCH2P(S)(CH2OH)2, was carried out by
literature method [22]. 1,3-propanediol was used as obtained
from Lancaster. Hexane, ethylacetate, dichloromethane
and tetrahydrofuran were distilled and dried by standard
procedures.
1
CH2)3O[N3P3F3(C6H5)2] (4). Yield: 0.08 g, 10%. NMR: H,
d 7.74–7.65 (m, 4H, C6H5), 7.40–7.32 (m, 6H, C6H5), 4.08–
4.03 (m, 4H, CH2O), 1.91 (quintet, 2H, –CH2–); 31P{1H}, d
24.70 [t (2JPNP = 44.4 Hz), P(C6H5)2], 12.74 [md (1JPF
=
895.0 Hz), OPF], 7.88 [mt (1JPF = 902.2 Hz), PF2]; 19F, d
ꢀ64.20 [md (1JPF = 908.4 Hz), OPF], ꢀ66.83 [md (1JPF
=
907.1 Hz), PF2], ꢀ67.44 [md (1JPF = 912.9 Hz), PF2]; 13C{1H},
d 30.46–30.14 (m, –CH2–), 63.57 (d, CH2O), 128.69–128.49
(m, o-C), 130.40–130.22 (m, m-C), 132.11–132.04 (m, p-C)
133.11 and 134.46 (s, ipso carbons). MS(FAB) [m/e (species)]:
766 (M+), 662 [N3P3(C6H5)2]O(CH2)3O[(N3P3(C6H5)2], 404
[N3P3F3(C6H5)2]O(CH2)3O, 362 [N3P3F3(C6H5)2]O. Anal.
Calcd. for C27H26O2P6N6F6 (%): C, 42.32; H, 3.42; N,
10.97. Found: C, 42.20; H, 3.28; N, 10.81.
4.2. Instrumentation
1H, 31P{1H}, 19F and 13C{1H} NMR spectra were recorded
using a JEOL JNM-LA 400 FT NMR and Bruker Spectrospin
DPX-300 spectrometers with CDCl3, as solvent. The chemical
shifts are reported with respect to the internal standards, TMS
(for 1H), 85% H3PO4 [for 31P{1H}], and CFCl3 (for 19F). Mass
spectra were obtained on a JEOL D-300 spectrometer in the
FAB mode. Elemental analyses were carried out Carlo-Erba
CHNO 1108 elemental analyzer. IR spectra were recorded as
The second compound which was obtained as white solid
was identified as ansa-{3,5-[O(CH2)3O]}[1,1-(C6H5)2]N3P3F2
1
(3). Yield: 0.04 g, 5%; mp: 98 8C. NMR: H, d 7.74–7.68 (m,
4H, C6H5), 7.41–7.31 (m, 6H, C6H5), 4.48–4.40 (m, 2H,
CH2O), 4.34–4.24 (m, 2H, CH2O), 2.18–2.07 (m, 2H, CH2P);
31P{1H}, d 26.88 [tt (2JPNP = 42.0 Hz), P(C6H5)2], 18.06 [md
(1JPF = 909.5 Hz), OPF]; 19F, d ꢀ71.92 [md (1JPF = 910.4 Hz),
OPF]; 13C{1H}, d 31.97 (m, –CH2–), 66.82–66.78 (m, CH2O),
128.61–128.36 (m, o-C), 130.60–130.32 (m, m-C), 131.84–
131.66 (m, p-C), 132.08 and 132.81 (s, ipso carbons). MS(FAB)
´ ´
KBr pellets on a Nicolet Protege 460 FT-IR spectrometer
operating at 400–4000 cmꢀ1
.

1052
A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
[m/e (species)]: 401 (M+), 324 N3P3F2(C6H5)[O(CH2)3O], 363
N3P3(C6H5)2[O(CH2)3O], 154 N3P3F1, 135 N3P3. Anal. Calcd.
for C15H16O2P3N3F2 (%): C, 44.90; H, 4.02; 10.47. Found: C,
44.81; H, 3.87; N, 10.40.
4.3.4. Reaction of the FcCH2P(S)(CH2OLi)2 with
compound 1
The diol, FcCH2P(S)(CH2OH)2 (0.88 g, 2.7 mmol) was
lithiated by adding n-BuLi (3.42 mL, 5.5 mmol) at ꢀ80 8C in
THF (20 mL). After 4 h of stirring, compound 1 (1.00 g,
2.7 mmol) dissolved in 20 mL of THF was added to the above
solution dropwise with constant stirring at ꢀ80 8C. The mixture
was allowed to reach room temperature over a period of 2 h, and
then stirred further for 12 h. Afterwards, the THF was
evaporated off, the mixture dissolved in dichloromethane
and the LiF formed was filtered off. The mixture was analyzed
by TLC and 31P{1H} NMR spectroscopy. The products were
purified by column chromatography over silica gel using
ethylacetate/hexane mixture as eluent. The analysis of the
fractions collected first (0.25 g, 28%) showed the presence of
ansa and spiro derivatives. Upon dissolving it in the
ethylacetate/hexane and on cooling to 4 8C yielded crystals
of spiro-[1,1-(C6H5)2][3,3-FcCH2P(S)(CH2O)2]N3P3F2 (8).
Yield: (0.11 g, 12%); mp: 199 8C. NMR: 1H, d 3.47 [d
(JPH = 11 Hz), 2H, FcCH2P], 4.17 (s, 5H, C5H5), 4.18–4.17 (m,
2H,C5H4), 4.31–4.23 (m, 2H, PCH2O), 4.35–4.30 (m, 2H,
C5H4), 4.87–4.84 (m, 2H, PCH2O), 7.42–7.38 (m, 4H, o-H of
C6H5), 7.49–7.44 (m, 2H, m-H of C6H5), 7.74–7.69 (m, 4H, p-H
of C6H5); 31P{1H}, d 24.54 [t (2JPP = 44 Hz), P(C6H5)2], 19.19
[d (3JPP = 15 Hz), P S], 14.04–13.25 (m, OPO), 4.98 [ddt
The third compound which obtained as a white solid was
identified as spiro-{1,1-[O(CH2)3O]}[1,1-(C6H5)2]N3P3F2 (2).
Yield: 0.07 g, 9%; mp: 144 8C. NMR: 1H, d 7.84–7.79 (m, 2H,
C6H5), 7.73–7.67 (m, 2H, C6H5), 7.47–7.31 (m, 6H, C6H5),
4.34–7.24 (m, 2H, CH2O), 4.04–3.95 (m, 2H, CH2O), 2.03–
1.90 (m, 2H, –CH2–); 31P{1H}, d 23.94 [t (2JPNP = 42.8 Hz),
P(C6H5)2], 12.05–11.52 (m, OPO), 6.78 [mt (1JPF = 906.3),
PF2]; 19F, d ꢀ66.72 [md (1JPF = 909.3 Hz), PF2]; 13C{1H}, d
31.94 (s, –CH2–), 66.80 (s, CH2O), 128.60–128.35 (m, o-C),
130.57–130.46 (m, m-C), 131.80–131.66 (m, p-C), 134.02 and
135.31 (s, ipso carbons). MS(FAB) [m/e (species)]: 401 (M+),
400 (M+ ꢀ H), 382 N3P3F(C6H5)2[O(CH2)3O], 324 N3P3F2
(C6H5)[O(CH2)3O], 247 N3P3F2[O(CH2)3O], 327 N3P3F2
(C6H5)2, 135 N3P3, 77 C6H5.
The fourth compound which obtained as a viscous liquid
was identified as dangling-[HO(CH2)3O](C6H5)2N3P3F3 (5).
Yield: 0.31 g, 39%. IR (DCM) (cmꢀ1): 3419 (s, broad, OH).
NMR: 1H, d 7.73–7.65 (m, 4H, C6H5), 7.42–7.31 (m, 6H,
C6H5), 4.12–4.07 (m, 2H, CH2O), 3.58 (t, 2H, –CH2OH), 1.76
(quintet, 2H, –CH2–), 2.41 (s, broad, 1H, –OH); 31P{1H}, d
24.91 [t (2JPNP = 44.4 Hz), P(C6H5)2], 12.94 [md (1JPF
=
900.6 Hz), OPF], 8.03 [mt (1JPF = 902.6 Hz), PF2]; 19F, d
(1JPF = 905 Hz, JPP = 72.7 and 45 Hz), PF2]; 19F, d ꢀ66.91
2
ꢀ63.99 [md (1JPF = 889.6 Hz), OPF], ꢀ66.66 [md (1JPF
=
[ddd (1JPF = 906 Hz, JPF = 12 and 6 Hz), PF2]; 13C{1H} d
3
917.4 Hz), PF2], ꢀ67.49 [md (1JPF = 902.4 Hz), PF2]; 13C{1H},
d 32.31 [d (J = 7 Hz), CH2], 57.88 (s, CH2OH), 64.77 [d
(J = 6 Hz), CH2O], 128.60–128.41 (m, o-C), 130.29–130.13
(m, m-C), 132.09–132.03 (m, p-C), 132.82 and 134.19 (s, ipso
carbons). MS(FAB) [m/e (species)]: 421 (M+), 404 N3P3F2
(C6H5)2[O(CH2)3], 344 N3P3F2(C6H5)[O(CH2)3O], 154 N3P3F,
135 N3P3. Anal. Calcd. for C15H16O2P3N3F2 (%): C, 42.77; H,
4.07; 9.98. Found: C, 42.59; H, 3.83; N, 10.18.
28.90 [d (JPC = 46 Hz), FcCH2P], 66.29 [d (JPC = 50 Hz),
PCH2O], 68.71 (s, b-C of C5H4), 69.03 (s, C5H4), 69.68 (s, g-C
of C5H4), 75.65 (s, a-C of C5H4), 128.59 [d (JPC = 14 Hz), o-C
of C6H5], 130.58 [d (JPC = 12 Hz), m-C of C6H5], 132.14 (s, p-
C of C6H5), 132.92 and 134.35 (s, ipso carbons). MS(FAB) [m/e
(species)]: 649 (M+), 476 N3P3F[FcCH2P(S)(CH2O)2], 306
+
FcCH2P(S)(CH2O)(CH2 ), 199 FcCH2, 154 N3P3F, 121
Fe(hC5H4), 77 C6H5. Anal. Calcd. for C25H25O2P4N3F2S1Fe1
(%): C, 46.25; H, 3.88; N, 6.47. Found: C, 46.16; H, 3.65, N,
6.32.
4.3.3. Reaction of monolithiated 1,3-propanediol with
compound 1
Further keeping the mixture at 0 8C for 4 days yielded a
precipitate which was characterized as endo-[1,1-(C6H5)2][3,5-
FcCH2P(S)(CH2O)2]N3P3F2 (6). Yield: (0.06 g, 7%); mp:
The 1,3-propanediol (0.22 g, 2.9 mmol) was monolithiated
in THF by the slow addition of n-BuLi (1.8 mL, 2.9 mmol) as
THF (40 mL) solution at ꢀ80 8C and was stirred for 6 h at
ꢀ80 8C. After 6 h, the gem-diphenylfluorophosphazene (1)
(1.05 g, 2.9 mmol) dissolved in THF (20 mL) was added to the
above solution at ꢀ80 8C and the mixture was allowed to reach
room temperature over a period of 2 h. After the stirring of
mixture at room temperature for 12 h, THF was evaporated off
and the residue was dissolved in dichloromethane to filter off
the LiF formed in the reaction. The mixture was analyzed by
TLC and purified by column chromatography over silica gel
using ethyl acetate/hexane mixture as eluent. The compound
which came out of the column around 17–25% of ethyl acetate
in hexane was characterized as the dangling derivative,
[HO(CH2)3O]N3P3F3(C6H5)2 (5) (0.86 g, 71%). The spectral
data of the compound obtained in this reaction was compared
with that the compound obtained in the reaction of dilithiated
propanediol with compound 1. This reaction also yielded traces
of other products ansa 3, spiro 2 and bridged 4 derivatives.
1
190 8C. NMR: H, d 2.86 [d (J = 11 Hz), FcCH2P], 3.85 (s,
5H, C5H5), 4.05 to 4.04 (m, 4H,C5H4), 4.21–4.12 (m, 2H,
CH2O), 4.61–4.55 (m, 2H, CH2O), 7.55–7.38 (m, 6H, C6H5),
7.74–7.69 (m, 2H, C6H5), 7.94–7.89 (m, 2H, C6H5); 31P{1H}, d
45.13 (s, P S), 25.41 [t (2JPP = 44.4 Hz), P(C6H5)2], 14.76 [dd
2
(1JPF = 954.8 Hz, JPNP = 44.4 Hz), OPF]; 19F, d ꢀ70.01 [md
(1JPF = 940.1 Hz), PF2]; 13C{1H}, d 27.03 (s, FcCH2), 65.35 (s,
CH2O), 68.66 (s, b-C of C5H4), 69.01 (s, C5H5), 69.80 (s, g-C
of C5H4), 128.86–128.55 (m, o-C of C6H5), 130.52–130.41 (m,
m-C of C6H5), 132.14 (s, p-C of C6H5) 132.45 and 132.11 (s,
ipso carbons of C6H5). MS(FAB) [m/e (species)]: 649 (M+), 476
N3P3F[FcCH2P(S)(CH2O)2], 307 FcCH2P(S)(CH2O)(CH2H),
199 FcCH2, 154 N3P3F, 121 Fe(C5H4). Anal. Calcd. for
C25H25O2P4N3F2S1Fe1 (%): C, 46.25; H, 3.88; N, 6.47. Found:
C, 46.35; H, 3.75, N, 6.40.
After the separation of the spiro and endo ansa compounds the
remaining residue after removal of solvent was characterized as

A.J. Elias et al. / Journal of Fluorine Chemistry 127 (2006) 1046–1053
1053
exo-[1,1-(C6H5)2][3,5-FcCH2P(S)(CH2O)2]N3P3F2 (7). Yield:
(0.05 g, 6%); mp: 182 8C. NMR: H, d 3.12 [d (J = 11 Hz),
solved by SHELXS-97 and refined by SHELXL-97 [24]. The
structure was refined against F2 with a full-matrix least-squares
algorithm. All non-hydrogen atoms were refined anisotropi-
cally. The X-ray data pertaining to data collection, crystal
system, and structure solution as well the selected bond
distances and angles for the compound 8 are given in Tables 2
and 3. Complete crystallographic information has been
deposited with the CCDC (deposition number CCDC
609231). Copies of the data can be obtained, free of charge,
on application to CCDC, 12 Union Road, Cambridge, UK
(fax: +44 1223 336033 or e-mail: deposit@ccdc.cam.ac.uk).
1
FcCH2P], 3.80 (s, 5H, C5H5), 4.16–4.14 (m, 4H, C5H4), 4.26–
4.18 (m, 2H, CH2O), 4.70–4.65 (m, 2H, CH2O), 7.50–7.31 (m,
6H, C6H5), 7.78–7.63 (m, 2H, C6H5), 7.98–7.91 (m, 2H, C6H5);
31P{1H}, d 47.55 (s, P S), 26.81 [t (2JPNP = 39.6 Hz), (C6H5)2],
2
14.28 [dd, OPF (1JPF = 920.8 Hz, JPNP = 40.1 Hz)]; 19F, d
ꢀ72.83 [md (1JPF = 912.9 Hz), OPF]; 13C{1H}, d 29.68 (s,
FcCH2), 64.97 (s, CH2O), 68.60 (s, b-C of C5H4), 69.11 (s,
C5H5), 69.85 (s, g-C of C5H4), 128.81–128.51 (m, o-C of C6H5),
130.57–130.46(m,m-CofC6H5), 132.24(s, p-CofC6H5)132.48
and 132.17 (s, ipso carbons of C6H5). MS(FAB) [m/e (species)]:
649 (M+), 476 N3P3F[FcCH2P(S)(CH2O)2], 307 FcCH2P(S)
(CH2O)(CH2H), 199 FcCH2, 154 N3P3F, 135 N3P3. Anal. Calcd.
for C25H25O2P4N3F2S1Fe1 (%): C, 46.25; H, 3.88; N, 6.47.
Found: C, 46.18; H, 3.75, N, 6.56.
Acknowledgements
A.J.E. thanks the Department of Science and Technology,
India (DST) for financial assistance in the form of a research
grant. Facilities provided by Department of Chemistry, IIT
Kanpur to K.M. during this work is gratefully acknowledged.
The second fraction obtained from column chromatography
was characterized as bridged derivative [(C6H5)2P3N3F3]
[OCH2(FcCH2)P(S)CH2O][(C6H5)2P3N3F3] (10) (0.14 g,
16%). Semi-solid charring around 102 8C. NMR: 1H, d
3.05–3.07 (m, 2H, FcCH2), 4.05–4.00 (m, 9H, Fc), 4.24–
4.16 (m, 4H, CH2O), 7.43–7.38 (m, 12H, C6H5), 7.73–7.67 (m,
8H, C6H5); 31P{1H}, d 40.28 (t, P S), 25.25 [t (2JPNP = 44 Hz),
P(C6H5)2], 13.09 [md (2JPNP = 917 Hz), OPF], 7.45 [mt
(2JPNP = 905 Hz), PF2]; 19F, d ꢀ66.65 [md (1JPF = 919 Hz),
PF2], ꢀ68.96 [md (1JPF = 938 Hz), PF2], ꢀ69.70 [md
(1JPF = 929 Hz), OPF]; 13C{1H} d 29.53 (s, FcCH2), 62.71
(s, CH2O), 69.59 (s, b-C of C5H4), 69.95 (s,C5H5), 70.49 (s, g-C
of C5H4), 76.59 (s, a-C of C5H4), 128.69–128.55 (m, o-C of
C6H5), 130.28 to 130.20 (m, m-C of C6H5), 132.22 ( p-C of
C6H5), 132.70 and 133.94 (s, ipso carbons). MS(FAB): 1014
(M+), 706 [P3N3F3][OCH2(FcCH2)P(S)CH2O][P3N3F3], 306
FcCH2P(S)(CH2O)(CH2–), 199 FcCH2. Anal. Calcd. for
C37H35O2P7N6F6SFe (%): C, 43.81; H, 3.48; N, 8.28. Found:
C, 43.58; H, 3.56, N, 8.36.
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The third fraction obtained from chromatography was
characterized as dangling derivative (C6H5)2P3N3F3[OCH2
(FcCH2)P(S)CH2OH] (9) (0.25 g, 29%). Semi-solid charring
around 120 8C. IR (nujol) (cmꢀ1): 3423 s (broad, OH), NMR:
1H, d 1.35 (s, 1H, OH), 3.05–3.08 (m, 2H, FcCH2), 3.88–3.81 (m,
2H, CH2O), 4.25–4.03 (m, 9H, Fc), 4.91–4.81 (m, 2H, CH2O),
7.71–7.18 (two set of multiplets, 10H, C6H5); 31P{1H}, d 40.46
(m, P S), 25.01 (m, P(C6H5)2), 13.39 [md (2JPNP = 921 Hz),
OPF], 7.58 [mt (2JPNP = 934 Hz), PF2]; 19F, d ꢀ66.54 [md
(1JPF = 902 Hz), PF2), ꢀ68.72 [md (1JPF = 928 Hz), PF2],
ꢀ69.50 [md (1JPF = 934 Hz), OPF]; 13C{1H} d 29.09 (FcCH2),
59.97–59.12 (m, CH2O), 62.98–61.74 (m, CH2O), 68.87 (s, b-C
of C5H4), 69.38 (s, C5H5), 69.85 (s, g-C of C5H4) 128.55 (m, o-C
of C6H5), 130.10 (m, m-C of C5H4), 132.14 (m, p-C of C5H4),
133.67 (s, ipso carbon). MS(FAB): 669 (M+). Anal. Calcd.
C25H26O2P4N3F3SFe (%): C, 44.86; H, 3.92; N, 6.28. Found: C,
44.70; H, 3.84; N, 6.15.
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4.4. X-ray diffraction studies
The X-ray diffraction data for compound 8 was collected on
an Enraf-Nonius CAD-4 diffractometer. The structure was
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