Syntheses and spectroscopic investigation of some cyclophosphazanes: Analysis of pseudo-triplet splitting

Article abstract of DOI:10.1002/hc.20229

Some new phosphoramidates, 1-3, and the corresponding cyclophosphazanes, 4-6, with formula Cl₂P(p-NHC₆H₄CH₃) 1, Cl₂P(O)(p-NHC₆H₄NO₂) 2, (CH ₃)₂NP

Full text of DOI:10.1002/hc.20229

Heteroatom Chemistry
Volume 17, Number 4, 2006
Syntheses and Spectroscopic Investigation
of Some Cyclophosphazanes:
Analysis of Pseudo-Triplet Splitting
Khodayar Gholivand, Zahra Shariatinia, Zahra Ahmadian Tabasi,
and Azadeh Tadjarodi
Department of Chemistry, Faculty of Sciences, Tarbiat Modarres University,
P.O. Box 14115-175, Tehran, Iran
Received 7 October 2004; revised 24 May 2005
researches [1–3], mainly because such molecules are
ABSTRACT: Some new phosphoramidates, 1–3,
good starting materials for polycyclic inorganic and
organometallic compounds [4,5]. The wide range ap-
plications of cyclophosphazanes in nucleophilic sub-
and the corresponding cyclophosphazanes, 4–6,
with formula Cl2P(p-NHC6 H CH3) 1, Cl2P(O)(p-
4
NHC6 H NO2) 2, (CH3)2NP(O)Cl(p-NHC6 H CH3)3,
4
4
stitution reactions on P Cl bonds [6,7], coordination
chemistry [8], and ring-opening polymerization re-
actions [9] causes a significant attraction to this area
of chemistry. There are many articles reporting the
synthesis and structure of phosphorus(III) [10–15]
and phosphorus(V) cyclophosphazane compounds
[16–21].
Johnson et al. [22] and others [23,24] reported
the synthesis of Cl2P(O)(p-NHC6H4NO2) and char-
acterized it only by 31P NMR spectroscopy and
melting point, respectively. Vesterager et al. [25]
prepared compound [(CH3)2NP(O)(p-NC6H4CH3)]2
from P(O)[N(CH3)2]3 and p-toluidine and character-
ized this molecule only by elemental analysis. Davis
et al. [26] obtained molecule [ClP(p-NC6H4CH3)]2
and identified it by IR, mass spectroscopy, and
elemental analysis.
[ClP(p-NC6 H CH3)]2 4, [ClP(O)(p-NC6 H NO2)]2 5,
4
4
and [(CH3)2NP(O)(p-NC6 H CH3)]2 6 were synthesized
4
and characterized by 1H, 13C, 31P NMR, IR, mass spec-
troscopy, and elemental analysis. A pseudo-triplet sig-
nal was observed in the 1H NMR spectrum of molecule
6 for the N(CH3)2 protons. The A6Aꢀ6 X2 spin sys-
tem was suggested for the pseudo-triplet pattern of
3JPNC H coupling in this molecule. Ab initio calcula-
tions were performed at the HF and B3LYP levels
of theory with 6-311G∗∗ standard basis set on the
geometry of compound 6. Also, the NMR chemical
shift calculations were done to compare the com-
puted results with the experimental ones. The calcu-
lated results are in good agreement with experimental
ꢁ
C
data.
2006 Wiley Periodicals, Inc. Heteroatom Chem
17:337–343, 2006; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20229
Ab initio NMR chemical shifts calculations are
extended in all areas of chemistry to determine the
configurations, conformations, and isomers [27–34]
and also to find the NMR parameters [35,36].
In this paper, we prepared some new cyclophos-
phazanes and their corresponding phosphorami-
dates. The 1H NMR spectrum of cyclophosp-
hazane 6 indicated a pseudo-triplet pattern for
31P–1H splitting. Ab initio calculations showed a
reasonable consistency with this splitting, and we
INTRODUCTION
The chemistry of small inorganic heterocycles of
the type (P N)2 are of great interest in recent
Correspondence to: Khodayar Gholivand; e-mail: gholi kh@
modares.ac.ir.
c
ꢁ
2006 Wiley Periodicals, Inc.
337

338 Gholivand et al.
39]. But the 1H NMR spectrum of compound 6 shows
correlate this coupling with the steric effects in this
compound.
a pseudo-triplet pattern of splitting for 12 protons
3
of the dimethylamine groups with JPNCH = 5.4 Hz
(Fig. 1). Our low-temperature dynamic NMR ex-
1
RESULTS AND DISCUSSION
periments on the H NMR spectrum of this com-
pound were done only to 223 K and in this tem-
perature the pseudo-triplet peak converts to a broad
signal.
Synthetic and Spectroscopic Aspects
Syntheses of compounds 1–6 were performed by
the reaction of phosphorus trichloride, phosphoryl
chloride, and N,N-dimethyl phosphoramidic dichlo-
ride with p-toluidine (in excess or in the presence
of an HCl scavenger such as triethylamine) and
p-nitroaniline. The phosphorus chemical shifts and
the JP X (X = H, C) coupling constants of compounds
1–6 are listed in Table 1. The general formula of
these molecules is shown in Scheme 1. Phosphorus-
31 NMR spectrum of molecule 1 indicates a sig-
nal at 150.68 ppm which towards down fields in
the corresponding cyclophosphazane 4 (with a sig-
nal at 201.51 ppm). The spectra of compounds 2
and 3 show the 31P signals at down fields relative
to the signals of their corresponding cyclophosphaz-
anes 5 and 6, respectively. The shielding of phospho-
rus atoms in molecules 5 and 6 can be attributed
to the increase of resonance interactions in these
compounds compare with their related monomers
2 and 3.
Meisel et al. already reported a similar phe-
nomenon for compound 7 with fine splitting of an
1
A3Aꢀ3MMꢀXXꢀspin system. The H NMR spectrum of
this compound shows a pseudo-triplet peak for the
SCH3 protons (3 JPSCH = 18.2 Hz). Also, the 13C NMR
spectrum of this molecule indicated a pseudo-triplet
for the SCH3 carbon atoms. Hagele et al. obtained
1
a calculated H NMR spectrum for this compound
by simplification of the A3Aꢀ3MMꢀXXꢀ spin system
to an A3Aꢀ3XXꢀ system with the assumption that
2 JP P = 140.0 Hz. The structure of pseudo-triplet they
obtained consists of two sharp outer parts, and the
central part is a quartet [40].
2 JPNH coupling constant in molecule (p-
CH3C6H4NH)P(O)Cl2 is 11.6 Hz [37] that increases
in compound 3 to 12.7 Hz. It seems that substitution
of chlorine atom by N(CH3)2 group causes more
interaction between phosphorus and nitrogen atoms
and thus increasing this coupling constant.
1
Because the 31P{ H} NMR spectrum of com-
pound 6 shows only a singlet signal, the two
phosphorus atoms are magnetically and chemically
equivalent (X2 spin system for two equal P atoms).
In reviewing the literature, the observed geometry
for four-membered ring crystalline cyclophosphaz-
anes is the cis configuration of the two P X moieties
(X = S [10], Se [41], and lone pair [13–15]). Thus,
we can conclude that perhaps only the cis isomer of
cyclophosphazanes is present in the solution. Fur-
3
The JPNCH coupling constant in compound
(CH3)2NP(O)Cl2 is 15.8 Hz [38,39] and it decreases
to 14.0 and 5.4 Hz in molecules 3 and 6, respectively.
This phenomenon is described as the formation of
partial multiple bonds between phosphorus and ni-
3
thermore, we did not observe any n JP (n= 4–6) for
trogen atoms that cause decreasing of JPNCH cou-
H
pling constant [37].
similar cyclophosphazanes [14,15,41]. This means
that the N(CH3)2 protons could not couple with the
phosphorus atom which is placed far from them
(5 JPNPNCH = 0 Hz). Therefore, the pseudo-triplet split-
Usually, a doublet peak have seen for methyl pro-
tons in compounds with the (CH3)2NP(O)XY skele-
3
ton and the JPNCH values depend on the X and Y
1
substituents vary in the range of 9.89–15.8 Hz [37–
ting pattern in the H NMR spectrum must be due
TABLE 1 The δ31P (ppm) and the JP X (X = H, C) Coupling Constants (Hz) for Compounds 1–6
Compound
δ31P
2J PNH
3J PNCH
2J P
3J P
4J P
5J P
2J P
Ci pso
C
Cor tho
Cmeta
Cpar a
1
2
3
4
5
6
d, 150.68
d, 6.34
oct, 17.21
s, 201.51
s, 1.31
7.1
10.6
12.7
s, 0
s, 0
–
–
–
14.0
–
–
5.4
s, 0
s, 0
2.8
s, 0
s, 0
s, 0
d, 5.4
s, 0
d, 2.1
d, 6.5
d, 9.0
d, 2.8
t, 7.7
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
s, 0
t, 8.5
s, 0
s, 0
hept, −1.94
t, 6.9
Heteroatom Chemistry DOI 10.1002/hc

Syntheses and Spectroscopic Investigation of Some Cyclophosphazanes 339
SCHEME 1 The formula of compounds 1–3 and corresponding cyclophosphazanes 4–6.
that the 13C NMR spectrum indicates a singlet peak
for the four carbon atoms of two N(CH3)2 groups.
One possibility for the formation of this pattern is
probably that six equal protons of one N(CH3)2 group
(A6) split by its near phosphorus atom to give a dou-
blet. Other six protons of another N(CH3)2 group
to the presence of two unequivalent N(CH3)2 groups.
In the solution, likely the low-rotational barrier along
the P N bonds cause the methyl groups in each
N(CH3)2 moiety convert to each other and, thus, we
1
31
observe only one singlet signal in the H{ P} NMR
spectrum of this compound. An interesting point is
FIGURE 1 The pseudo-triplet splitting pattern in the 1H NMR spectrum of compound 6, [(CH3)2NP(O)(p-NC6H4CH3)]2.
Heteroatom Chemistry DOI 10.1002/hc

340 Gholivand et al.
(Aꢀ6) couple with their P atom to produce a dou-
blet. Combination of these two doublet peaks gives a
pseudo-triplet signal. Based on these arguments, we
can propose the A6Aꢀ6X2 spin system for this splitting.
Carbon-13 NMR spectrum of compound 2
showed a doublet signal for 3 JP Cortho (9.0 Hz), but the
spectrum of its corresponding dimmer 5 indicated a
singlet. The spectra of cyclophosphazanes 4 and 6
show a triplet with 3 JP Cortho = 7.7 and 6.9 Hz, respec-
tively, but there is a singlet in compound 5. The only
triplet signal for ipso carbon with 2 JP Cipso = 8.5 Hz
was observed in compound 4, while in compounds 5
and 6 it is a singlet peak. It should be mentioned that
only in molecule 5 with p-nitroaniline substituent,
all phosphorus–carbon couplings are vanished.
Computational Aspects
In order to further investigate on the structure of
compound 6 and evaluation of our prediction on the
geometry of this molecule, we performed ab initio
calculations to obtain the optimized geometry of this
molecule. The preferred geometry for similar com-
pounds of these series is the cis configuration of
two P O moieties, therefore, full optimizations on
the cis geometry of this compound were done us-
ing Hartree–Fock (HF) and B3LYP methods with
6-311G∗∗ standard basis set give two equal struc-
tures. The optimized structure is shown in Fig. 2 and
Scheme 2 and indicates that the two N(CH3)2 groups
have different spatial orientations. This means that
the carbon atoms connected to N7 have different
spatial orientation relative to the two other carbon
SCHEME 2 The atom-labeling scheme for the optimized
structure of compound 6 (H atoms are omitted for clarity).
atoms linked to N11. Therefore, our computations
confirm the predicted structure for compound 6 and
we can suggest the A6Aꢀ6X2 spin system for pseudo-
triplet splitting pattern in the 1H NMR spectrum.
1
The H, 13C, and 31P NMR chemical shift cal-
culations for this compound are done using HF
and B3LYP methods and 6-311G∗∗, 6-311+G∗∗, and
6-311++G∗∗ basis sets, and results are summa-
rized in Table 2. To calculate 1H NMR chemical
shifts, UHF/6-311++G∗∗ is rather suitable. Carbon-
13 chemical shift calculations show that B3LYP/6-
311++G∗∗ and B3LYP/6-311+G∗∗ give accurate
results. The data show the best result for 31P chemi-
cal shift by B3LYP/6-311G∗∗.
EXPERIMENTAL
All reactions were carried out under argon atmo-
sphere. Solvents and other chemical reagents were
from Merck, Sigma, Aldrich, and Fluka. Solvents
were dried by refluxing with the appropriate drying
agent and distilled before use. Melting points were
determined with a Gallenkamp apparatus. NMR
spectra were run at room temperature (298 K) on
a Bruker 500 (Avance DRS) spectrometer by dissolv-
ing 30 mg of sample in 0.5 mL of deuterated solvents
at 500.13 MHz (1H), 202.45 MHz (31P), and 125.77
MHz (13C) in different solvents. 1H, 13C, and 31P chem-
ical shifts were referenced to internal TMS and exter-
nal 85% H3PO4 standards, respectively. The infrared
spectra were recorded on a Shimadzu model IR-
60 spectrometer. Elemental analysis was performed
FIGURE
2 The optimized structure of molecule 6,
[(CH3)2NP(O)(p-NC6H4CH3)]2, obtained from the ab initio
calculations at HF/6-311G** and B3LYP/6-311G** levels (H
atoms are omitted for clarity).
Heteroatom Chemistry DOI 10.1002/hc

Syntheses and Spectroscopic Investigation of Some Cyclophosphazanes 341
TABLE 2 Experimental and Calculated 31P, 1H, and 13C NMR Chemical Shifts (ppm) for Compound 6
UHF/
UHF/
UHF/
B3LYP/
B3LYP/
B3LYP/
Exp. NMR
6-311G∗∗
6-311+G∗∗
6-311++G∗∗
6-311G∗∗
6-311+G∗∗
6-311++G∗∗
31P, −1.95
8.98
61.30
59.33
3.78
59.21
59.33
1H, 2.28
2.85
1.55
1.83
6.34
6.48
20.61
33.67
1.69
1.94
6.52
6.73
20.25
33.52
1.73
1.96
6.56
6.77
20.27
33.54
1.21
1.47
5.98
6.11
9.07
22.13
1.46
1.89
6.22
6.34
21.1
35.99
1.50
1.92
6.27
6.39
21.19
36.13
7.05
7.1
13C, 20.83
36.57
118.27
130.28
133.25
133.47
130.46
131.74
135.48
141.08
131.74
132.41
136.39
142.57
131.76
132.43
136.43
142.62
118.95
120.19
123.92
129.56
128.39
130.75
135.99
140.5
128.43
130.78
136.05
140.59
(CDCl3): δ = 7.30 (d, 3 JH H = 9.0 Hz), 7.58 (d, NH,
2 JPNH = 10.6 Hz), 8.27 (d, 3 JH H = 9.0 Hz). 13C NMR
(CDCl3): δ = 144.19 (s, Cpara), 142.54 (s, Cipso), 125.70
(s, Cmeta), 119.07 (d, 3 JP Cortho = 9.0 Hz). 31P NMR
(CDCl3): δ = 6.34 (d, 2 JPNH = 10.6 Hz). Anal. Calcd. for
C6H5Cl2N2O3P (254.99): C, 28.26; H, 1.98; N, 10.99.
Found: C, 28.23; H, 1.96; N, 11.03%.
using a Heraeus CHN-O-RAPID elemental analysis.
Mass spectra were obtained on a 70 eV Finnigan
mat (EI model) spectrometer. N,N-Dimethyl phos-
phoramidic dichloride was prepared according to
the literature method [38].
N-(p-Methylphenylamino)dichlorophosphine,
Cl2 P(p-NHC6 H4 CH3) 1
N,N-Dimethyl-Nꢀ-4-methylphenyl
Phosphoramidic Chloride,
(CH3)2NP(O)Cl(p-NHC6 H4CH3 3
To a solution of 2.14 g (20 mmol) p-toluidine in di-
ethyl ether (15 mL) under argon atmosphere and stir-
ring, 1.37 g (10 mmol) phosphorus trichloride was
added dropwise at −10◦C. After 5 h stirring, CCl4
(15 mL) was added to the filtered solution and di-
ethyl ether was removed under vacuum to give com-
pound 1. Yield, 1.52 g (73%), mp 185–186◦C; IR: 3490
(N H), 2915, 1439, 1379, 1164, 814 (P N), 710, 630,
471 cm−1; 1H NMR (CCl4, CDCl3): δ = 2.32 (s, p-CH3),
6.99 (d, 3 JH H = 8.0 Hz), 7.16 (d, 3 JH H = 8.0 Hz), 7.29
(d, 2 JPNH = 7.1 Hz); 13C NMR (CCl4, CDCl3): δ = 135.10
(d, 2 JP Cipso = 6.5 Hz), 133.65 (d, 5 JP Cpara = 2.1 Hz),
1.62 g (10 mmol) of N,N-dimethyl phosphoramidic
dichloride was dissolved in toluene (20 mL) and
the solution flask was placed in an ice bath. Then,
2.14 g (20 mmol) of p-toluidine was added drop-
wise to the solution. After 3 h stirring, the mix-
ture was kept at −10◦C for 45 h. After filtration and
removing the solvent, an oily compound was ob-
tained which was purified by column chromatogra-
phy method with ethyl acetate:n-hexane (1:1). Yield
1.98 g (85%); IR: 3135 (N–H), 3010, 1605, 1504,
1450, 1377, 1271, 1218 (P O), 991 (P Nar), 948, 808,
3
130.10 (s, Cmeta), 121.7 (d, JP Cortho = 5.4 Hz), 20.82
(s, p-CH3);31P NMR (CCl4, CDCl3): δ = 150.68 (d,
2 JPNH = 7.1 Hz); Anal. Calcd. for C7H8Cl2NP (208.03):
C, 40.42; H, 3.88; N, 6.73. Found: C, 40.40; H, 3.85;
N, 6.75%.
1
745 (P Nal), 577 cm−1; H NMR (CDCl3): δ = 2.25
3
(s, p-CH3), 2.76 (d, JPNCH = 14.0 Hz, 2CH3), 6.35
2
(d, JPNH = 12.7 Hz, NH), 7.01 (d, 3 JH H = 9.1 Hz);
13C NMR (CDCl3): δ = 136.23 (s, Cpara), 132.37 (s,
3
C
ipso), 129.82 (s, Cmeta), 119.14 (d, JP Cortho = 2.8 Hz),
36.81 (d, JPCH = 2.8 Hz), 20.68 (s, CH3); 31P NMR
(CDCl3): δ = 173.21 (oct, n JP H = 13.6 Hz). Anal. Calcd.
for C9H14ClN2OP (232.65): C, 46.46; H, 6.07; N, 12.04.
Found: C, 46.43; H, 6.06; N, 12.07%.
2
N-(p-Nitrophenyl)phosphoramidic Dichloride,
Cl2P(O)(p-NHC6 H4NO2) 2
A mixture of 4.60 g (30 mmol) phosphoryl chloride
and 1.38 g (10 mmol) p-nitroaniline was heated for
2 h at 40◦C. The product was washed with petroleum
ether (20 mL) and was dried under vacuum. Yield,
2.12 g (83%), mp 149–151◦C; IR: 3400 (N H), 2925,
2605, 1590, 1512 (NO2), 1336 (NO2), 1282, 1249
(P O), 1100, 1075, 942 (P N), 845, 586, 557 cm−1;
2,4-Dichloro-1,3-bis(4-methylphenyl)-1,3,2,4-
diazadiphosphetidine, [ClP(p-NC6 H4CH3)]2 4
A mixture of 1.07 g (10 mmol) p-toluidine and
1.01 g (10 mmol) triethylamine was dissolved in n-
hexane (30 mL) and slowly added to a solution of
31
1H{ P} NMR (CDCl3): δ = 7.3 (d, 3 JH H = 9.0 Hz),
7.58 (s, NH), 8.27 (d, 3 JH H = 9.0 Hz). 1H NMR
Heteroatom Chemistry DOI 10.1002/hc

342 Gholivand et al.
1.37 g (10 mmol) phosphorus trichloride in n-hexane
(7 mL). A vigorous reaction occurred with the for-
mation of a white mass (salt of triethylamine). After
refluxing for 8 h, the mixture was cooled to room
temperature and filtered under argon atmosphere.
The filtrate was concentrated and kept at −10◦C for 2
days to give the product. Yield, 2.69 g (78%), mp 180–
181◦C; IR: 2980, 2910, 1570, 1197, 1020, 806 (P N),
482 cm−1; 1H NMR (CDCl3): δ = 2.33 (s, 2p-CH3), 6.94
(d, 3 JH H = 8.0 Hz), 7.11 (d, 3 JH H = 8.0 Hz); 13C NMR
(s, Cpara), 133.25 (s, Cipso), 130.28 (s, Cmeta), 118.28
3
(t, JP Cortho = 6.9 Hz ), 36.57 (s, 2N(CH3)2), 20.83 (s,
3
2p-CH3). 31P NMR (CDCl3): δ = −1.94 (hept, JP
=
H
5.4 Hz). 31P{ H} NMR (CDCl3): δ = −1.94 (s); m/z
(EI) (%): 392 (4) [M]+, 243 (10) [C9H13N2O2P2]+, 196
(37) [C9H13N4O2P2]+, 153 (40) [C7H8NOP]+, 136 (80)
[C7H7NP]+, 107 (26) [C7H9N]+, 106 (36) [C7H8N]+,
91 (C7H7]+, 77 (20) [C6H5]+, 49 (100) [H2PO]+; Anal.
Calcd. for C18H26N4O2P2 (392.38): C, 55.10; H, 6.68;
N, 14.28. Found: C, 55.07; H, 6.65; N, 14.30%.
1
(CDCl3): δ = 134.97 (t, 2 JP Cipso = 8.5 Hz), 132.93 (s,
3
C
para), 129.96 (s, Cmeta), 117.21 (t, JP Cortho = 7.6 Hz),
20.66 (s, 2p-CH3); 31P NMR (CDCl3): δ = 201.51 (s);
m/z (EI) (%): 342 (12) [M]+, 307 ([C14H14N2ClP2]+,
25), 276 ([C14H14N2ClP]+, 5), 241 ([C14H14N2P]+,
35), 171 ([C7H7NClP]+, 20), 136 ([C7H7NP]+, 74),
107 ([C7H8N]+, 100); Anal. Calcd. for C14H14Cl2N2P2
(343.13): C, 49.00; H, 4.11; N, 8.16. Found: C, 48.97;
H, 4.09; N, 8.13%.
Computational Methodology
All quantum chemical calculations were performed
with the GAUSSIAN-98 program suite [42]. The ge-
ometry of compound 6 is fully optimized using HF
and DFT (B3LYP) levels of theory in the gas phase.
The standard 6-311G∗∗ is applied in these calcula-
tions. The optimizations are followed by calcula-
tions of the harmonic and vibrational frequencies.
No imaginary frequency is obtained in these calcu-
lations. NMR calculations are performed at the HF
and DFT (B3LYP) levels of theory with 6-311G∗∗, 6-
311+G∗∗, and 6-311++G∗∗ standard basis sets. Cal-
ibration of the calculated chemical shifts of com-
2,4-Dichloro-1,3-bis(4-nitrophenyl)-1,3,2,4-
diazadiphosphetidine-2,4-dioxide,
[ClP(O)(p-NC6 H4NO2)]2 5
This compound was prepared in the same way as
molecule 2, but the mixture was heated for 4 h at
90◦C. Yield 3.94 g (90%), mp 158–159◦C; IR: 3335,
2835, 2625, 1586, 1512 (NO2), 1466, 1344 (NO2),
1295 (P O), 1129, 983, 853, 733, 670 cm−1; 1H
1
pound 6 was performed by computing the H and
13C chemical shifts of TMS and 31P chemical shift
of H3PO4 as standards and then subtraction of these
values from the calculated chemical shift values of
compound 6.
3
NMR (CD3CN): δ = 6.89 (d, JH H = 9.0 Hz), 8.08 (d,
3 JH H = 9.0 Hz); 13C NMR (CD3CN): δ = 151.32 (s,
C
C
para), 139.64 (s, Cipso), 126.01 (s, Cmeta), 115.05 (s,
ortho); 31P NMR (CD3CN): δ = 1.31 (s); m/z (EI) (%):
ACKNOWLEDGMENTS
300 ([M-C6H5N2O2]+, 4), 138 ([C6H4N2O2]+, 65), 122
([N2O2P2]+, 3), 108 ([NO2P2]+, 62), 92 ([NOP2]+, 28),
79 ([HOP2]+, 26), 63 ([P2]+, 100), 48 ([HOP]+, 24);
Anal. Calcd. for C12H8Cl2N4O6P2 (437.07): C, 32.98;
H, 1.84; N, 12.82. Found: C, 32.96; H, 1.81; N, 12.79%.
We would like to express our thanks to Dr.
H. Sabzyan in Chemistry Department of Isfahan
University and to Dr. M. Pouramini in Chemistry
Department of Shahid Beheshti University for their
helpful discussions. Also, we thank Mr. A. R. Ghaderi
for his helps in the running computer programs.
2,4-Dimethylamino-1,3-bis(4-methylphenyl)-
1,3,2,4-diazadiphosphetidine-2,4-dioxide,
[(CH3)2NP(O)(p-NC6 H4CH3)]2 6
REFERENCES
This compound was prepared in the same way as
compound 3, but after filtration, the solution was
concentrated and placed at room temperature for 1
month. Colorless and needle crystals were obtained.
Yield 2.37 g (60%), mp 250–252◦C, IR: 3025, 2923,
2850, 1600, 1503, 1472, 1442, 1296, 1257 (P O),
1185, 986 (P N), 947, 826, 638 cm−1; 1H NMR
[1] Haagenson, D. C.; Stahl, L. Inorg Chem 2001, 40,
4491.
[2] Chandrasekhar, V.; Vivekanadan, K.; Nagendran, S.;
Andavan, G. T. S.; Weathers, N. R.; Yarbrough, J. C.;
Cordes, A. W. Inorg Chem 1998, 37, 6192.
[3] Schranz, I.; Moser, D. F.; Stahl, L.; Staples, R. J. Inorg
Chem 1999, 38, 5814.
[4] Chiverz, T.; Parvez, M.; Schatte, G. Inorg Chem 2001,
40, 540.
[5] Chen, T. Q.; Duesler, E. N.; Paine, R. T.; No¨th, H. Inorg
Chem 1997, 36, 802.
3
(CDCl3): δ = 2.29 (s, 2p-CH3), 2.85 (t, JPNCH = 5.4
Hz, 2N(CH3)2), 7.04 (d, 3 JH H = 8.2 Hz), 7.09 (d,
31
3 JH H = 8.2 Hz). 1H{ P} NMR (CDCl3): δ = 2.29 (s,
[6] Kumar, N. S.; Kumara, S. K. C. Polyhedron 2004, 23,
979.
[7] Allen, C. W. Chem Rev 1991, 91, 133.
2p-CH3), 2.85 (s, 2N(CH3)2), 7.04 (d, 3 JH H = 8.2 Hz),
7.09 (d, 3 JH H = 8.2 Hz). 13C NMR (CDCl3): δ = 133.47
Heteroatom Chemistry DOI 10.1002/hc

Syntheses and Spectroscopic Investigation of Some Cyclophosphazanes 343
[8] Allcock, H. R.; Turner, M. L. Macromolecules 1993,
[29] Farcasiu, D.; Lukinskas, P.; Hancu, D. J Mol Model
2000, 6, 171.
26, 3.
[9] Manners, I. Angew Chem, Int Ed Engl 1996, 35, 1602.
[10] Kommana, P.; Vittal, J. J.; Kumara, S. K. C. Polyhe-
dron 2003, 22, 843.
[11] Bell, S. A.; Meyer, T. Y.; Geib, S. J. J Am Chem Soc
2002, 124, 10698.
[12] Janca, M.; Necas, M.; Zak, Z.; Prihoda, J. Polyhedron
2001, 20, 2823.
[13] Stahl, L. Coord Chem Rev 2000, 210, 203.
[14] Viijulatha, M.; Kumara, S. K. C.; Vittal, J. J.; Koh, L. L.
Polyhedron 1999, 18, 2249.
[30] Dransfeld, A.; Flock, M.; Nguyen, M. T. J Mol Model
2000, 6, 289.
[31] Tossell, J. A. Phys Chem Minerals 1998, 25, 453.
[32] Ernst, L.; Fresenius, J. Anal Chem 1997, 357, 494.
[33] Kock, M.; Junker, J. J Mol Model 1997, 3, 403.
[34] Heydenreich, M.; Koch, A.; Kleinpeter, E.;
Zimmermann, T. Fresenius J. Anal Chem 1997,
357, 517.
[35] Jasznnski, M.; Dolgonos, G.; Dodziuk, H. Theor Chem
Acc 2002, 108, 240.
[15] Viijulatha, M.; Kumaraswamy, S.; Kumara, S. K. C.;
Engelhardt, U. Polyhedron 1999, 18, 2557.
[16] Chivers, T.; Krahn, M.; Schatte, G. Inorg Chem 2002,
41, 4348.
[17] Tirree, J.; Gudat, D.; Nieger, M.; Niecke, E. Angew
Chem 2001, 113, 3115.
[18] Kerth, J.; Werz, U.; Maas, G. Tetrahedron 2000, 56,
35.
[19] Novomestska, V.; Marek, J.; Prihoda, J. Polyhedron
1999, 18, 2723.
[20] Romaneko, V. D.; Sanchez, M. Coord Chem Rev 1997,
158, 275.
[21] Kaukorat, T.; Neda, I.; Schmutzler, R. Coord Chem
Rev 1994, 137, 53.
[22] Johnson, O.; Murray, M.; Woodward, G. J Chem Soc,
Dalton Trans 1989, 821.
[23] RewCastle, G. W.; Atwell, G. J.; Baguley, B. C.; Denny,
W. A. Eur Pat Appl EP 73155 (ClC07F9.64), 2 March
1983, NZ Appl 19811521, August 1981, 36 pp.
[24] Heinz, L. K.; Marx, J.; Weise, A.; Boettcher, H. (VEB
Filmfabrik wolfen, Fotochemisches Kombinat) Ger.
(East) DD 230094 (ClG03C7/16), 20 November 1985,
Appl 271217, 20 December 1984, 12 pp.
[25] Vesterager, N. O.; Dyrnesli, R.; Pedersen, E. B.;
Lawesson, S. O. Synthesis Commun 1972, 548.
[26] Davis, A. R.; Dronsfield, A. T.; Haszeldine, R. N.;
Taylor, D. R. J Chem Soc, Perkin Trans I 1973, 379.
[27] Drosihn, S.; Porzel, A.; Brandt, W. J Mol Model 2001,
7, 34.
[36] Schreckenbach, G.; Ziegler, T. Theor Chem Acc 1998,
99, 71.
[37] Gholivand, K.; Ghadimi, S.; Naderimanesh, H.;
Forouzanfar, A. Mag Reson Chem 2001, 39, 684.
[38] Keat, R.; Shaw, R. J Chem Soc, A 1968, 703.
[39] Gholivand, K.; Mahmoudkhani, A. H.; Khosravi, M.
Phosphorus, Sulfur and Silicon 1995, 106, 173.
[40] Meisel, M.; Pauli, F.; Donath, C. In 31P-NMR Spec-
tral Properties in Compounds Characterization and
Structural Analysis; Quin, L. D.; Verkade, J. G. (Eds.);
VCH: New York, 1994; p. 129.
[41] Lief, G. R.; Carrow, C. J.; Stahl, L.; Staples, R. J.
Organometallics 2001, 20, 1629.
[42] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria,
G. E.; Robb, M. A.; heeseman, J. R.; Zakrzewski, V. G.;
Montgomery, J. A.; Stratmann Jr., R. E. J.; Burant, C.;
Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin,
K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone,
V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli,
C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson,
G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman,
J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.;
Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.;
Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara,
A.; Challacombe, M. P.; Gill, M. W.; Johnson, B.;
Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez,
C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A.
Gaussian 98, Revision A.9; Gaussian, Inc.: Pittsburgh,
PA, 1998.
[28] Ecker, G.; Kalchhauser, H.; Lawtrakul, L.; Wolschann,
P. Monatsshefte fur Chemie 2001, 132, 373.
Heteroatom Chemistry DOI 10.1002/hc