New phosph(V)azane ligand as a bidentate donor in the synthesis of one novel organometallic tin(IV) compound

Article abstract of DOI:10.1080/10426500701506390

The new ligand {[(C6H5NH)P(O)H](NC6H5)[(C6H5NH)P(O)H]} (2) was synthesized by heating bis(anilino)phosphine oxide (C6H5NH)2P(O)H (1) at 110°C and elimination of aniline. The treatment of 2 with SnBu2 Cl2 in the presence of triethylamine (TEA) in dry THF y

Full text of DOI:10.1080/10426500701506390

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New Phosph(V)azane Ligand
as a Bidentate Donor in
the Synthesis of One Novel
Organometallic Tin(IV)
Compound
a
a
Abbas Tarassoli , Ginous Emami & Ziba
a
Khodamoradpur
a
Chemistry Department, College of Science , Shahid
Chamran University , Ahvaz, Iran
Published online: 25 Sep 2007.
To cite this article: Abbas Tarassoli , Ginous Emami & Ziba Khodamoradpur (2007)
New Phosph(V)azane Ligand as a Bidentate Donor in the Synthesis of One Novel
Organometallic Tin(IV) Compound, Phosphorus, Sulfur, and Silicon and the Related
Elements, 182:11, 2497-2505, DOI: 10.1080/10426500701506390
To link to this article: http://dx.doi.org/10.1080/10426500701506390
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Phosphorus, Sulfur, and Silicon, 182:2497–2505, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701506390
New Phosph(V)azane Ligand as a Bidentate Donor
in the Synthesis of One Novel Organometallic
Tin(IV) Compound
Abbas Tarassoli
Ginous Emami
Ziba Khodamoradpur
Chemistry Department, College of Science, Shahid Chamran University,
Ahvaz, Iran
The new ligand {[(C6H5NH)P(O)H](NC6H5)[(C6H5NH)P(O)H]} (2) was synthe-
◦
sized by heating bis(anilino)phosphine oxide (C6H5NH)2P(O)H (1) at 110 C
and elimination of aniline. The treatment of
2 with SnBu2 Cl2 in the
presence of triethylamine (TEA) in dry THF yielded the novel compound
n
2
Bu Sn{[Et3NH(NPh)P(O)H](NPh)p(O)H]}2 (3) in which the phosphazane ligand
acts as a bidentate ligand. The products have been characterized by means of
1
13
31
119
elemental analysis, IR, MS, and multinuclear NMR ( H, C, P, and
Sn)
spectroscopy. The spectroscopic data are consistent with the bounding of the
phosph(V)azane ligand through both oxygen and phosphorus atoms to Sn(IV) center
in the final compound 3. TEA is used as a base in order to deprotonate the phosp-
+
−
+
hazane ligand and is separated as Et3NH Cl , whereas HTEA exists in the title
product 3 and is acting as a charge balancing and H-bond structure directing agent.
Keywords 119Sn NMR; bidentatebidentate; charge charge balancing; H-bonding;
phosph(V)azane; TEA
INTRODUCTION
Amino substituted phosphazanes, both phosph(III)azanes and
phosph(V)azanes are potential intermediates for the synthesis of
a wide variety of phosphazane compounds becaue of their N H
1
bond functionality. In this way, phosphor(V)azans substituted with
chalcogens (O, S, Se, or Te) have prompted inorganic chemists interest
in studying their coordination chemistry.2 We were interested in
Received March 1, 2007; accepted April 9, 2007.
Support of this work by the Shahid Chamran University, Ahvaz, Iran (grantNo.
AT1384), is gratefully acknowledged.
Address correspondence to Abbas Tarassoli, Chemistry Department, College of Sci-
ence, Shahid Chamran University, Ahvaz, Iran. E-mail: tarassoli@scu.ac.ir
2497

2
498
A. Tarassoli et al.
studying those categories of these P(V) N derivatives containing
3
−6
oxygen because of their ease of synthesis and stability.
In our ongoing work, we have re-examined the formation reaction
of bis(anilino)phosphine oxide (C6H5NH)2P(O)H (1). This ligand has
7
already been obtained by hydrolysis of (PhNH)2P which shown in Eq. 1.
Oligomerization of 1 by thermal elimination of aniline yielded the
new ligand {[(C6H5NH)P(O)H](NC6H5)[(C6H5NH)P(O)H]} (2) that is
reported here.
In order to investigate the coordinating ability and the behavior of
this new ligand towards organotin(IV) moieties, 2 was lead let to react
n
with SnBu2 Cl2 to obtain the new organometallic tin(IV) derivative 3.
In recent years, there has been considerable interest in the coor-
dination chemistry of Sn(IV) derivatives and continues to receive at-
tention mainly due to the reactivity, interesting structural features
and anticancer activity of some organotin(IV) compounds. For instance,
they have been known as having a specific action on mitochondrial
oxidative phosphorylation, and also, in recent years many triorgano-
and diorganotin compounds have been tested for their in vitro activity
against a large variety in vitro activity against a large variety of tu-
8
−14
mor lines.
Among the interesting tin-coordinative derivatives are
1
3
phosphorus-based acids containing Sn O bond. Our oxygen oxygen-
containing phosph(V)azane ligand that can bond to dibutyldichlorotin
precursor through both donor atoms N and O simultaneously is as one of
the attractive cases in this field in which the unprecedented compound
3
has been formed.

New Phosph(V)azane Ligand
2499
The resulting products were characterized by elemental analysis, as
1
13
31
119
well as MS, IR and multinuclear NMR ( H, C, P, Sn) spectroscopy.
EXPERIMENTAL
Materials and Methods
All experiments were performed under nitrogen using standard
Schlenk techniques. The solvents were purified and dried as indi-
cated: Tetrahydrofurane was treated with KOH and freshly distilled
twice from sodium before use. Diethyl ether and n-hexane were treated
with calcium chloride and distilled over sodium. Aniline was dis-
tilled from CaH2 and stored over molecular sieves. NEt3 was distilled
over MgSO4. Toluene was distilled over sodium. CHCl3 and CH2Cl2
n
were distilled from P4O10. Phosphorus trichloride and Bu2 SnCl2 were
used as purchased from Merck Co. NMR spectra were recorded on a
1
Bruker Avance 500 MHz at ambient temperature. H (500.13 MHz)
1
3
and C NMR (125.77 MHz) were recorded using DMSO as a sol-
1
vent with TMS as an external standard for H NMR and DMSO
1
3
31
119
for C NMR. P spectra (202.45 MHz) and
Sn spectrum (195.50
MHz) were referenced to external H3PO4 85% and Me4Sn respec-
tively. IR spectra were measured on a Bomem FT-IR spectropho-
tometer. FAB(+) mass spectra were recorded using a JEOL SX-102A
instrument. Elemental analysis (C, H, N) was performed by the
microanalytical service of N.I.O.C. Research Institute of Petroleum
Industry.

2
500
A. Tarassoli et al.
Preparation of (PhNH) P(O)H (1)
2
PCl3 (5 ml, 0.057 mol) in 10 ml toluene was added slowly under N2
to a stirred solution of PhNH2 (26.02 ml, 0.285 mol) in 60 ml of dry
◦
◦
toluene at 0 C. The reaction mixture was warmed up slowly to 25 C.
After 2 h water (0.057 mol) in an H2O-CHCl3 solution was added slowly
◦
to the mixture. Then the mixture was stirred at 80 C for another 2 h.
PhNH3 Cl was filtered off from the hot reaction mixture. The solvent
was removed, and the white product was washed with cold toluene,
+
−
◦
then recrystallized from ethanol (yield 84%), m.p. 160 C. Anal. Calc.
for C12H13N2PO: C, 62.07; H, 5.64; N, 12.06%. Found: C, 62.09; H, 5.58;
N, 12.02%.
Synthesis of {[(PhNH)P(O)H](NPh)[(PhNH)P(O)H]} (2)
(
PhNH)2P(O)H (0.5 g, 2.115 mmol) was dissolved in 100 ml of dry
◦
toluene under N2 atomsphere and then was refluxed at 110 C for 3 h.
The mixture was filtered from the hot reaction mixture. The solvent was
removed and the white product was washed with cold toluene. Then the
remaining solid was recrystallized from CH2Cl2 (yield 52%), m.p. 165 C.
Anal. Calc. for C18H N3P2O2: C, 58.22; H, 5.15; N, 11.31%. Found: C,
◦
19
58.28; H, 5.12; N, 11.29%.
n
Synthesis of Bu Sn{[Et NH(NPh)P(O)H](NPh)[(PhN)P(O)H]}
2
3
2
(
3)
n
SnBu2 Cl2 (0.081 gr, 0.269 mmol) was dissolved in 10 ml of dry THF,
and added dropwise to a mixture of 2, (0.2 g, 0.539 mmol) and 1 ml of
◦
NEt3 (excess) in 50 ml of dry THF under N2 at 25 C. Then the mix-
+
−
ture was stirred for 48 h. NEt3H Cl was filtered off. The solvent was
removed and the pale yellow residue was washed twice with diethyl
ether, hexane and 1 ml of cold THF and dried under vacuum for 24 h
◦
to yield essentially pure 3 (yield 70.6%), m.p. 210 C dec. Anal. Calc. for
C56H84N8P4O4Sn: C, 57.1; H, 7.1; N, 9.5%. Found: C, 56.6; H, 6.7; N,
8.9%.
All attempts in growing single crystal of 3 suitable for X-ray crystal-
lography were unsuccessful at this stage.
RESULTS AND DISCUSSION
In this workarticle, we prepared bis(anilino)phosphine oxide
(
C6H5NH)2P(O)H (1) according to an improved procedure with a

New Phosph(V)azane Ligand
2501
better yield than that previously reported, one15 that which is shown
in scheme Scheme 1.
The new phosph(V)azane ligand 2 reported here was synthe-
sized as shown in Scheme 1. As we have suggested, the reac-
tion proceeds via an aniline elimination between two monophosp-
◦
hazane 1 by heating at 110 C to form the dinuclear phosphazane
{
[(C6H5NH)P(O)H](NC6H5)[(C6H5NH)P(O)H]} (2). This compound is
moderately soluble in a few solvents such as THF, DMSO, CH2Cl2
and slightly soluble in CHCl3, EtOH and (CH3)2CO. It is very sta-
ble solid and no decomposition was observed, even when it was
exposed to the air for one week. It was also stable in the above
solvents.
SCHEME 1
n
2
In continuation, 2 was reacted with SnBu Cl2 to obtain the unprece-
dented product 3 (Eq. 2) in the ratio of 2:1 in the presence of an excess of
◦
triethylamine (TEA). The reaction was carried out at 25 C in dry THF

2
502
A. Tarassoli et al.
TABLE I Infrared Data for Compounds 1–3
Compound ν (HNEt3)
ν (N H)
ν (P H)
ν (P O)
ν (Sn O) ν (Sn N)
1
2
3
3191
3334
2369
2365
2355
1175
1150–1091
1114–1071
3462
563
433
and the pale-yellow product was obtained.
n
2
{[(PhNH)P(O)H](NPh)[(PhNH)P(O)H]} + SnBu Cl2 + NEt3 →
2
n
+
−
Bu Sn{[Et3NH(NPh)P(O)H](NPh)[(PhN)P(O)H]}2 + NEt3H Cl (2)
2
The adduct compound 3 is moderately soluble in THF and DMSO and
slightly soluble in CHCl3, EtOH and (CH3)2CO; and it is also is stable in
when exposure exposed of to air for at least one day. The title compounds
1
–3 were characterized by IR (Table I), Mass and multinuclear NMR
1
13
31
119
( H, C, P, Sn) spectroscopy (Tables II–IV) and elemental analysis
C, H, N).
(
Infrared spectra data given in Table II indicate that ligand 2 shows
strong bands in the regions 3334, 2365, 1635–1497, and 1150–1091
−
1
cm , assigned to N H, P H, C C and P O vibrations, respectively.
IR spectrum for 3 shows that the P O stretching shifted by almost
−1
3
0 cm to the lower frequency upon coordination, as a result of decrease
in the P O bond order. The appearance of two new bands at 563 and 433
−
1
cm , which are assigned to Sn O and Sn N, respectively, supports the
bonding of central tin atom to oxygen and nitrogen. The IR spectrum
−
1
also clearly showed the absence of the ligand N H band at 3334 cm
and exhibited the presence of a new broad band centered at 3462 cm−1,
which is attributed to protonated triethylamines. These information
proves the binding through N and O from dinuclear ligand to Sn(IV)
center.
The mass spectrum of 3 was recorded with FAB positive source. The
mass data (m/z 57, 102, 269, 155, 212, 459, 539) are easily related to
+
the proposed structures, with the normal loss of n-Bu, HNEt3 , and
fragments arising from the Bu2Sn moities and the ligand.
1
13
31
119
Tables II–IV list H, C, P, and Sn chemical shifts and coupling
1
13
constants for 1–3 compounds. The H and C NMR spectra of 2 and
confirmed the identity of the compounds, showing the expected inte-
gration and multiplicities (Table II). The H NMR of 2 exhibits phenyl
protons in the region of δ 6.62–7.33 ppm (complex multiplet, area 15)
and P H protons appears as a doublet at δ 6.71 ppm (doublet, area 2).
3
1
1
1
JPH = 633 Hz for 2 and JPH = 635 Hz for 3 are characteristic coupling

New Phosph(V)azane Ligand
2503
TABLE II 1H NMR Data of Compounds 1–3 in Me
SO-d
6
2
Compound
P
H
NPh
N
H
HNEt3
Sn Bu
1
7.28
(
6.5–7.5
8.09
d, 1JPH =
(m, 10H) (d, 2JPNH =
596 Hz, 1H)
8.92 Hz, 2H)
2
3
6.71
(
6.62–7.33 8.31
(m, 15H) (broad 2H)
d, 1JPH =
633 Hz, 2H)
7.05
6.44–7.49
(m, 30H)
1.15 (t, 3J =
0.85(t, 3JHH
(
6
d, 1JPH =
7.24 Hz, 18H, =7.21 Hz, 6H,
35 Hz, 4H)
CH3)
CH3, δ)
3
1.28 (m, 3JHH
= 7.38 Hz, 4H,
CH2, γ )
2
1
.97 (m, J =
5.7 Hz, 12H,
CH2)
0.18 (broad,
NH)
1.53 (m, 3JHH
= 7.40 Hz, 4H,
CH2, β)
1
.64 (m, 3JHH
=
7.49 Hz, 4H,
CH2, α)
constants for these types of compounds. The spectrum of 3 shows that
the butyl protons attached to tin appear as a complex signal ( multi-
plet, area 6) in the range of δ 0.85–1.64 ppm and the phenyl protons (
multiplet, area 30) at δ 6.44–7.49 ppm.
+
The presence of HTEA protons at 1.15, 2.97, and 10.18 ppm, to-
gether with the absence of the characteristic NH signal of the ligand,
+
suggested the occurrence of protonated HTEA cations. Triethylamine
was applied to deprotonate NH groups of the ligand but on the basis
1
of IR and H NMR evidence it exists in the final product 3. It may be
+
assumed that HTEA cation has a charge-balancing role and is acting
as an H-bond structure-directing agent. Similar situation is reported
TABLE III 13C{ H} NMR Data of Compounds 1–3 in Me
1
SO-d
Sn Bu
2
6
Compound
Ph
HNEt3
1
146.0 (Ci)
29.4 (Co), 118.3 (Cm), 115.9 (Cp)
146.7, 140.8, 130.1, 129.3, 123.8,
18.4, 117.8, 115.6
146.6, 130.1, 129.3, 122.6, 121.2,
18.4, 117.4, 115.3
1
2
3
1
45.9 (CH2),
39.5(CH3)
9.3 (Cδ), 14.2 (Cγ ),
26.0 (Cβ ), 28.0 (Cα)
1

2
504
A. Tarassoli et al.
TABLE IV 119Sn{ H}, 31P and 31P{ H} NMR data of compounds 1–3
1
1
2 6
in Me SO-d
δ (31P) (ppm)
δ
31
P( H) (ppm)
1
δ (119Sn) (ppm)
Compound
1
−4.07
−4.07
2
1
JPNH = 9.11 Hz
JPH = 590 Hz
2
3
1.34
1.38
1.52
1
JPH = 631 Hz
1.52
−218.22
1
JPH = 637 Hz
in the synthesis of conventional zeolites such as phosphate16−−17 and
1
8
triethylammonium benzenne-1,3,5-tricarboxylato (pyridine) zinc(II).
1
3
1
The C H spectrum of 2 showed eight signals characteristic of ter-
minal and bridging phenyl groups which appeared also in the spectrum
of 3. In addition, there are six signals that related to butyl and TEA
groups in compound 3. The 13C H NMR results show that terminal
phenyls are similar to those in compound 3.
1
3
1
In the P NMR spectrum of 2 only one signal occurs as a doublet at
δ 1.34 ppm, which is in the region associated with P(V) oxide species.
1
The relatively large JPH coupling constant (631 Hz) is also consistent
3
1
1
with that of a directly directly-bonded hydrogen. In the P{ H} NMR
spectrum of 3, only one signal is seen at 1.52 ppm in the region asso-
31
ciated with P(V) environment. P NMR coupled with proton displays
1
one doublet ( JP H = 637 Hz), which is consistent with the presence of
the P-H bond. We obtained no evidence for the involvement of this bond
during the course of reaction, under the conditions of our experiment.
It is interesting to note that, 31P NMR data exhibit identical chemical
1
3
environment for both phosphorus atoms and these data along with
C
NMR data reveal that some type of mechanism is involved which equal-
ize phosphorus atoms. We suggest that this is related to HNEt3 moiety,
which is being intrachangedinterchanged on nitrogen atoms in donor
ligands.
1
19
1
Sn{ H} NMR spectrum of 3 contains only one sharp singlet at
−
218 ppm indicating the formation of a single species, with the tin-
1
19 resonance appearing at lower frequency than that of its dibutyltin
19
dichloride precursor (+122 ppm in CH2Cl2). The coordination number
1
19
of six around the tin atom in 3 is also supported by its
Sn NMR
1
2,20−23
chemical shift.
The NMR spectra were also recorded in CDCl3
as a non-coordinative solvent, and interestingly the results were the
same with the data in DMSO and only the intensity of peaks were lower

New Phosph(V)azane Ligand
2505
because of less solubility. The quantitative determination of chloride in
showed the lacking of chloride in the product.
3
CONCLUSION
It is concluded, from MS, IR and NMR studies that the new
phosph(V)azane ligand [(C6H5NH)P(O)H](NC6H5)[(C6H5NH)P(O)H]
(
2) in the presence of an excess of triethylamine acts as a biden-
n
tate ligand bonding through oxygen and nitrogen atoms to give Bu
2
Sn{[Et3NH(NPh)P(O)H](NPh)[(PhN)P(O)H]}2 (3). This is the only
+
isolable product with HTEA which is playing an important role by in-
trachanginginterchanging between nitrogen atoms.
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