Synthesis and characterization of a novel phosph(V)azane-tin(IV) complex

Article abstract of DOI:10.1080/104265090517253

The reaction of bis(anilino)phosphine oxide (C₆H ₅NH)₂P(O)H, 1 with Bu₂ⁿSnCl ₂ in the presence of an excess of triethylamine (TEA) in dry tetrahydrofurane (THF) yields the novel N,O-bonded

Full text of DOI:10.1080/104265090517253

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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Synthesis and Characterization
of a Novel Phosph(V)azane-
Tin(IV) Complex
Abbas Tarassoli a & Ziba Khodamoradpur a
a Chemistry Department , College of Science, Shahid
Chamran University , Ahvaz, Iran
Published online: 21 Dec 2010.
To cite this article: Abbas Tarassoli & Ziba Khodamoradpur (2005) Synthesis and
Characterization of a Novel Phosph(V)azane-Tin(IV) Complex, Phosphorus, Sulfur, and
Silicon and the Related Elements, 180:2, 527-532, DOI: 10.1080/104265090517253
To link to this article: http://dx.doi.org/10.1080/104265090517253
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Phosphorus, Sulfur, and Silicon, 180:527–532, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090517253
Synthesis and Characterization of a Novel
Phosph(V)azane-Tin(IV) Complex
Abbas Tarassoli
Ziba Khodamoradpur
Chemistry Department, College of Science, Shahid Chamran University,
Ahvaz, Iran
The reaction of bis(anilino)phosphine oxide (C H NH) P(O)H, 1 with BunSnCl
2
6
5
2
2
in the presence of an excess of triethylamine (TEA) in dry THF yields the novel
N,O-bonded tin complex BunSn[NPh(O)P(H)NPh(HNEt )] , 2. TEA is used as
3
2
2
a base to deprotonate the phosphazane ligand and is separated as Et NH+Cl−,
3
whereas HTEA+ exists in the final product 2 and act as a charge balancing and
H-bond structure–directing agent. This new compound has been fully characterized
1
31
119
by means of IR, MS, and multinuclear ( H, P, and
Sn NMR) spectroscopy.
Keywords 119Sn NMR; bis(anilino)phosphine oxide; chelated compounds; substitution
reactions; tin complexes
Phosphazanes are an established class of P N compounds and are
known for their stability and ease of synthesis.1−3 The nature of the
highly polar P N bond with P- and N-donor sites makes a com-
pound of this kind versatile in both coordination and organometallic
chemistry.4−7 Although a few phosphazanes have been used as ligands
for main-group elements, their coordination chemistry is so far largely
unexplored.4,5 In particular the interaction between tin atom and P-
containing ligands is not well established.8
Herein, bis(anilino)phosphine oxide, 1 is employed as a precursor
which can form a dianionic ligand of type 3.5 We considered it of interest
to synthesize a new organotin compound 2 containing this competitive
P-, N-, and O-donor ligand.
These studies on the coordination chemistry of the phosph(V)azane
oxide with both soft and hard coordination sites may help to unravel
Received June 1, 2004; in final form July 20, 2004.
Support of this work by the Shahid Chamran University, Ahvaz, Iran (project No. 217)
is gratefully acknowledged.
Address correspondence to Abbas Tarassoli, Chemistry Department, College of Sci-
ence, Shahid Chamran University, Ahvaz, Iran. E-mail: tarassoli a@cua.ac.ir
527

528
A. Tarassoli and Z. Khodamoradpur
SCHEME 1
some interesting aspects of the mechanisms by which these complexes
form and behave.
RESULTS AND DISCUSSION
(C6H5NH)2P(O)H, 1 is prepared according to Eq. (1):
PCl3 + 5PhNH2 → (PhNH)2P(O)H + 3PhNH3Cl
(1)
The interaction of PCl3 with PhNH2 in a mole ratio of 1:5 re-
sults in the stepwise replacement of PhNH and finally formation of
(PhNH)3P, which is converted to (PhNH)2P(O)H upon addition of H2O
in a controlled hydrolysis reaction with the elimination of aniline (yield;
84%).
(PhNH)2P(O)H has already been obtained in excess of 60% yield by
hydrolysis of (PhNH)3P or [(PhNH)2P]2NPh.9 It seems that the direct
hydrolysis of the product which is reported here (Eq. (1)) is more con-
venient and in a better yield than the previously reported one. The
spectroscopic data are shown in the Experimental section.
In the 31P NMR spectrum a signal at δ-4.07 occurs, which is in the
region associated with P(V) oxide species. The relatively large 1JPH cou-
pling constant (590–610 Hz) also is consistent with that of a directly
1
bonded hydrogen. δP and JPH data agree well with those reported for
(C6H5NH)2P(O)H,9 also characterized as the phosphine oxide. Further

Phosphazane Tin Complex
529
characterization by IR and 1H NMR spectroscopic techniques was made
for 1.
Compound 1 was allowed to react with di-n-butyltin dichloride in the
ratio of 2:1 in presence of an excess of TEA to form Bun2Sn[(NPh)(O)P(H)
NPh(HNEt3)]2 2 (Eq. (2)). The reaction was carried out at 25◦C in dry
THF and the resulting pale yellow product was extensively studied by
MS and IR spectrometry as well as 1H, 31P, and 119Sn NMR techniques
(cf. Experimental section). It is notable that quantitative determination
of chloride in 2 showed the lacking of chloride in the product.
The P O stretching vibrations in IR spectrum shifted by almost
100 cm−1 to lower frequencies is coordination as a result of decrease
in the P O bond order. The appearance of two new bands at 529 and
476 cm−1 which is assigned to Sn O and Sn N, respectively, supports
the bonding of the central tin atom to oxygen and nitrogen. The IR
spectrum also clearly showed the absence of the ligand N H band at
3191 cm−1 and exhibited the presence of a new broad band centered at
3438 cm−1 which is attributed to protonated triethylamines.
1
The H NMR spectrum of 2 shows that the butyl protons attached
with tin as a complex multiplet are in the range of δ 0.85–1.60 ppm.
The presence of HTEA+ protons at 1.18, 3.04, and 10.28 ppm, 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
1
but based on the above IR and H NMR evidences TEA exists in the
final product 2. It may be assumed that HTEA+ cation has a charge-
balancing role and is acting as a H-bond structure–directing agent.
Similar situation is reported in the synthesis of conventional zeolites
such as phosphates10,11 and triethylammonium benzene-1,3,5- tricar-
boxylato (pyridine) zinc (II).12
1
In the 31P{ H} NMR spectrum of 2, only one signal is seen at
0.87 ppm in the region associated with P(V) environment, which is
flanked by Sn satellites (2JPSn = 125 Hz). 31P NMR coupled with pro-
ton displays one doublet (1JPH = 633 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.

530
A. Tarassoli and Z. Khodamoradpur
1
119Sn{ H} NMR spectrum of 2 contains only one sharp singlet at
−182 ppm indicating the formation of a single species, with the tin-
119 resonance appearing at lower frequency than that of its dibutyltin
dichloride precursor (+122 ppm in CH2Cl2).13 The coordination number
of six around the tin atom in 2 is also supported by its 119Sn NMR
chemical shift.14−17
The MS spectrum of 2 was recorded with FAB-positive source. The
mass data are easily related to the proposed structure, with the normal
loss of n-Bu, HNEt+, and fragments arising from the Bu2Sn entity and
3
the ligand.
All attempts in growing single crystal of 2 suitable for X-ray crystal-
lography were unsuccessful at this stage.
In conclusion, we have shown that the reaction of 1 with dibutyltin
dichloride in the presence of an excess of triethylamine has exclusively
led to the novel N,O-chelated complex 2, as the only isolable product
with HTEA+ which is residing in the interlayer space and playing an
important role as structural directing agent. More research work is
currently in progress to develop these types of chemistry.
EXPERIMENTAL
All experiments were performed under nitrogen using standard
Schlenk techniques. The solvents were purified and dried as indicated:
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 distilled from
CaH2 and stored over molecular sieves, NEt3 was distilled over MgSO4,
toluene was distilled over sodium, chloroform was distilled from P4O10,
and phosphorus trichloride, Bun2SnCl2 and absolute ethanol were used
as purchased from Merck Co.
NMR spectra were recorded on a Bruker Avance 500 MHz at ambi-
ent temperature. The chemical shifts were referenced to external TMS
for 1H NMR (500.13 MHz), H3PO4 85% for 31P NMR (202.45 MHz)
and Me4Sn was used as an external standard in 119Sn NMR (186.50
MHz). IR spectra were measured on a Bomem FT-IR spectropho-
tometer. FAB(+) mass spectrum was recorded using a JEOL SX-102A
instrument.
Preparation of (C6H5NH)2P(O)H (1)
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

Phosphazane Tin Complex
531
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 the hot reaction mixture. The solvent was
removed and the white product was washed with cold toluene, then
recrystallized from ethanol (yield 84%), mp 160◦C.
IR (KBr): 3191 (s, NH), 3032–3092 (Ph), 2369 (m, sh, P H), 1175
(P O), 749–690 (CH) cm−1. 1H NMR (25◦C, (CD3)2 SO, ppm): 7.50–6.50
2
1
(m, 10H, Ph), 8.09 (d, JPNH = 8.92 Hz, 2H, NH), and 7.28 (d, JPH
=
596 Hz, 1H, P H). 31P NMR (25◦C, (CD3)2SO, ppm): −4.07 (doublet of
triplet, 1JPH = 612 Hz, 2JPNH = 9.19 Hz).
Synthesis of Bun2 Sn [NPh (O)P(H) NPh (HNEt3)]2 (2)
Bun2SnCl2 (0.130 gr, 0.431 mmol) was dissolved in 10 mL of dry THF,
and added dropwise to a mixture of (C6H5NH)2P(O)H, 1, (0.2 gr, 0.862
mmol) and 1 mL of NEt3 (excess) in 50 mL of dry THF under N2 at
25◦C. Then the mixture 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 2. (yield 67%), mp 223◦C dec.
IR (KBr): 3438 (broad, NH), 3053 (Ph), 2359 (m, sh, P H), 1093
(P O), 749–683 (Ph), 598 (Sn C), 529 (SnP O), 476 (Sn N) cm−1. MS:
m/z 463, 269, 102, 57, 31.
3
1H NMR (25◦C, (CD3)2SO, ppm): 0.85 (t, JHH = 7.37 Hz, 6H, Bu),
3
3
1.18 (t, JHH = 7.29 Hz, 18H, HNEt3), 1.25 (m, JHH = 7.29 Hz, 4H,
Bu), 1.56 (m, 3JHH = 7 Hz, 4H, Bu), 1.60 (m, 3JHH = 7 Hz, 4H, Bu), 3.04
3
1
(quartet, JHH = 6.64 Hz, 12H, HNEt3), 6.70 (d, JPH = 633 Hz, 2H,
P H), 6.45–7.30 (m, 20H, Ph), 10.28 (s, broad, 2H, HNEt3). 119Sn{ H}
1
NMR (25◦C, (CD3)2SO, ppm): −182 (s). 31P{ H} NMR (25◦C, (CD3)2SO,
1
ppm): 0.87(s, 2JPSn = 125 Hz). 31P NMR: 0.87 (d, 1JPH = 637 Hz).
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