Synthesis and spectroscopic characterization of novel aryl- dithiofluorophosphonate derivatives and X-ray studies of [(4-CH 3OC 6H 4)(F)P(S)S][PH 4P+]

Article abstract of DOI:10.1080/10426507.2012.685667

Potassium and tetraphenylphosphonium salts of novel aryldithiofluorophosphonic acids were synthesized. Lawesson's Reagent was allowed to react with KF in acetonitrile to yield the potassium salt of p-methoxyphenyldithiofluorophosphonic acid. Treatment of

Full text of DOI:10.1080/10426507.2012.685667

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Synthesis and Spectroscopic
Characterization of Novel Aryl-
Dithiofluorophosphonate Derivatives and
X-Ray Studies of [(4-CH3OC6H4)(F)P(S)S-]
[PH4P+]
Ertuğrul Gazi Sağlam a , Ömer Çelik b , Hamza Yılmaz c & Nurcan
Acar c
a Department of Chemistry , Bozok University , 66200 , Yozgat ,
Turkey
b Department of Physics , Dicle University , 21280 , Diyarbakır ,
Turkey
c Department of Chemistry , Ankara University , 06100 , Tandoğan ,
Ankara , Turkey
Accepted author version posted online: 23 Apr 2012.Published
online: 06 Aug 2012.
To cite this article: Ertuğrul Gazi Sağlam , Ömer Çelik , Hamza Yılmaz & Nurcan Acar (2012)
Synthesis and Spectroscopic Characterization of Novel Aryl-Dithiofluorophosphonate Derivatives
and X-Ray Studies of [(4-CH3OC6H4)(F)P(S)S-][PH4P+], Phosphorus, Sulfur, and Silicon and the Related
Elements, 187:11, 1339-1346, DOI: 10.1080/10426507.2012.685667
To link to this article: http://dx.doi.org/10.1080/10426507.2012.685667
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Phosphorus, Sulfur, and Silicon, 187:1339–1346, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.685667
SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION
OF NOVEL ARYL-DITHIOFLUOROPHOSPHONATE
DERIVATIVES AND X-RAY STUDIES OF
[(4-CH3OC6H4)(F)P(S)S−][PH4P+]
1
2
3
¨
Ertug˘rul Gazi Sag˘lam, Omer C¸ elik, Hamza Yılmaz,
and Nurcan Acar3
1Department of Chemistry, Bozok University, 66200, Yozgat, Turkey
2Department of Physics, Dicle University, 21280, Diyarbakır, Turkey
3Department of Chemistry, Ankara University, 06100 Tandog˘an, Ankara, Turkey
GRAPHICAL ABSTRACT
Abstract Potassium and tetraphenylphosphonium salts of novel aryldithiofluorophosphonic
acids were synthesized. Lawesson’s Reagent was allowed to react with KF in acetonitrile to
yield the potassium salt of p-methoxyphenyldithiofluorophosphonic acid. Treatment of the latter
with tetraphenylphosphonium chloride resulted in the formation of the tetraphenylphosphonium
salt. The structures of the compounds were elucidated by FTIR, 1H, 13C, 19F, and 31P NMR
spectroscopy as well as by ESI-mass spectrometry. The molecular and crystal structure of the
tetraphenylphosphonium salt, determined by single crystal X-ray diffraction, is also presented.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Dithiophosphonic acid; phosphonodithioic acid; dithiofluorophosphonic acid;
dithiofluorophosphonate; Lawesson’s reagent; X-ray structure determination
INTRODUCTION
Perthiophosphonic anhydrides1 like the Lawesson’s Reagent (LR) are well known to
react with alcohols,2,3 amines,4,5 Grignard Reagents,6 and anhydrous alkaline metal fluo-
rides.7 The products are reported to be promising to find future uses in fields like agricultural
pest control,8 chemotheraphy,9 synthesis of novel antibiotics,10 and metal extraction.11,12
Received 5 January 2012; accepted 1 April 2012.
The authors gratefully acknowledge the financial assistance of Technical Research Council of Turkey (grant
number TBAG 110T016, TUBITAK) and Ankara University Research and Development Fund.
Address correspondence to Hamza Yılmaz, Department of Chemistry, Faculty of Science, Ankara University,
Tandog˘an, 06100 Ankara, Turkey. E-mail: hyilmaz@science.ankara.edu.tr
1339

˘
E. G. SAGLAM ET AL.
1340
Among the compounds containing a S P S group, those which are fluoro-substituted on
phosphorus13,14 and those with fluorinated alkyl or aryl groups15,16 appear to have attracted
little attention. Especially, the last 10 years have become rather infertile in terms of the
phosphonyl fluorides.17
Here we report on the reaction of LR with dry KF (Scheme 1) to yield the potassium
salt of p-methoxyphenyl dithiofluorophosphonic acid 1.
Scheme 1
The product was further allowed to react with tetraphenylphosphonium chloride to
give the corresponding tetraphenylphosphonium salt 2 (Scheme 2).
Scheme 2
The compositions of the compounds were studied by elemental analysis and their
1
structures were derived from IR, H, 13C, 19F, and 31P NMR spectriscopic and ESI-MS
studies. The structure of 2 was confirmed for the solid state by X-ray crystallography.
RESULTS AND DISCUSSION
Mass Spectra
The mass spectra obtained by an ESI source does not display discrete signals at-
tributable to the whole salts, as expected. The anion, observed in the anion mode, ap-
pears to remain unchanged in the ionization step with m/z value of 221.4 (calculated for
C7H7FOPS2, 221.2). The cation of compound 2 was observed in the cation mode and
appears at m/z = 339.1 (calculated for C24H20P, 339.4).
Infrared Spectra
The prominent characteristic IR-bands of the two compounds are given in the Ex-
perimental section. The characteristic asymmetric (as) and symmetric (s) νP bands are
S
observed at 689–698 cm−1 and 658–689 cm−1, respectively. Characteristic νP F bands are
observed at 737 cm−1 and 721 cm−1 for 1 and 2, respectively. The data support the structures
suggested in Schemes 1 and 2.

SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION
1341
Table 1 19F, 31P, 1H and 13C NMR data for the anion in compounds 1 and 2ꢁ
1
2
δ
19F
1JPF
31P
−29.4
1027.2
129.8
14.8
−25.9
1028.3
127.5
δ
3JPH
δ1H o-H
m-H
N
OMe
δ
1JPC
2JPF
C-o
2JPC
C-m
3JPC
C-p
4JPC
OMe
13.8
a
7.83
6.82
8.72
3.63
6.85
8.80
3.78
135.6
115.8
26.2
131.4
14.5
112.5
15.3
13C C-i
133.5
117.3
25.4
131.2
14.6
113.8
14.0
161.5
3.0
161.5
b
53.7
54.6
aδ31P = 24.2 (Ph4P+). bSignal overlaps with that of Ph4P+ protons.
NMR Spectra
1
NMR spectroscopic data (19F, 31P, H, and 13C) and signal patterns are given in
Table 1. Due to the solubility properties, the NMR spectra for 1 were recorded in D2O and
those for 2 in CD3OD. The data observed and in particular the direct P-F coupling constant
are in agreement with those reported in the literature.18–20 In the 1H NMR spectrum of 2,
the multiplet at 7–8 ppm corresponds to the protons of the Ph4P+ group. The signals for
the aromatic protons of the anion are superimposed with this multiplet. In the 13C NMR
spectrum of 1, the two-bond coupling between the carbon and fluorine and also the direct
C-P coupling constant compare well with the reported values for similar structures.21,22
Molecular and Crystal Structure of Compound 2
The structures of the cation and the anion in the crystal of compound 2 are shown in
Figure 1.
Selected atom distances and bond angles are listed in Table 2. The distances of
the phosphorus atom P1 to the directly bonded carbon atoms C1, C7, C13, and C19
are 1.788(10), 1.783(10), 1.805(12), and 1.824(11) Å, respectively. These data are in
good agreement with previous findings.23 For the phosphorus atom in the anion P2, the
corresponding distances to the directly bonded atoms P2-C25, P2-F and P2-S1, and P2-S2
are 1.791(13), 1.671(7), 1.929(5), and 1.848(7) Å, respectively.
The puckering amplitudes of the centroids of the rings, namely Cg1, Cg2, Cg3,
Cg4, and Cg5, were found to be 2.9, 2.2, 2.5, 3.5, and 4.2 Å, respectively.24 The shortest
intramolecular distance and dihedral angle between the centroids Cg1–Cg5(x, y, z) are
4.923(7) Å and 62.06◦, respectively. The corresponding values for Cg2–Cg5 (1−x, 1/2+y,

˘
E. G. SAGLAM ET AL.
1342
Figure 1 ORTEP view of the molecular structure of cation and anion in compound 2 with atom numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level.
1/2-z) are 4.132(7) Å and 34.87◦. The data relating to similar distances and dihedral angles
are given in Table 2.
. . .
Two intra- and intermolecular C-H S type hydrogen bonds become evident and the
. . .
relevant parameters are listed in Table 2. The donor-acceptor distances for C26-H26 S2,
. . .
. . .
. . .
C30-H30 S1, C27-H27 S1, and C22-H22 S2 are 3.408(16), 3.283(13), 3.464(15),
and 3.401(21) Å, respectively. The π-electron clouds of the various rings seem also to
be involved in the hydrogen bonding interactions. Assuming the centroids (Cg(n)) of the
. . .
rings as imaginary atoms, six different C-H Cg(n) bonds, two intramolecular, and four
intermolecular, can be located and the respective parameters are given in Table 2.
The dihedral angles between the five planar phenyl rings R1, R2, R3, R4, and R5 are
given in Table 3. The rings are labeled as indicated in Figure 1.
EXPERIMENTAL
Analytical grade LR, potassium fluoride, and tetraphenylphosphonium chloride were
purchased from Acros (Geel, Belgium) and used directly without further purification. Ace-
tonitrile, diethyl ether, and methanol, were purchased from Merck (Darmstadt, Germany).
Acetonitrile was distilled and dried before use.
Mass spectra were recorded with a Waters 2695 Allonce micromass spectrometer
with APCI/ESI ionizing attachment. Melting points were measured with a Gallenkamp
apparatus using a capillary tube. 1H, 13C, 19F, and 31P NMR spectra were recorded with a
400 MHz Varian Mercury 400 High Performance Digital FT-NMR spectrometer in D2O (1)
or CD3OD (2). SiMe4 (1H, 13C) and 85% H3PO4 (31P) were used as internal and external
standard, respectively. 19F chemical shifts are given with respect to trifluoroacetic acid as

1343

˘
1344
E. G. SAGLAM ET AL.
Table 3 Dihedral angles between rings for compound 2
Plane–plane
Dihedral angle (◦)
C1-C2-C3-C4-C5-C6 [R1, Cg1] - [R2, Cg2] C7-C8-C9-C10-C11-C12
C1-C2-C3-C4-C5-C6 [R1, Cg1] - [R3, Cg3] C13-C14-C15-C16-C17-C18
C1-C2-C3-C4-C5-C6 [R1, Cg1] - [R4, Cg4] C19-C20-C21-C22-C23-C24
C1-C2-C3-C4-C5-C6 [R1, Cg1] - [R5, Cg5] C25-C26-C27-C28-C29-C30
C7-C8-C9-C10-C11-C12 [R2, Cg2] - [R3, Cg3] C13-C14-C15-C16-C17-C18
C7-C8-C9-C10-C11-C12 [R2, Cg2] - [R4, Cg4] C19-C20-C21-C22-C23-C24
C7-C8-C9-C10-C11-C12 [R2, Cg2] - [R5, Cg5] C25-C26-C27-C28-C29-C30
C13-C14-C15-C16-C17-C18 [R3, Cg3] - [R4, Cg4] C19-C20-C21-C22-C23-C24
C13-C14-C15-C16-C17-C18 [R3, Cg3] - [R5, Cg5] C25-C26-C27-C28-C29-C30
C19-C20-C21-C22-C23-C24 [R4, Cg4] - [R5, Cg5] C25-C26-C27-C28-C29-C30
73.60 (37)
72.90 (35)
81.05 (42)
73.98 (37)
60.72 (46)
77.84 (37)
34.65 (43)
59.57 (50)
60.84 (42)
60.78 (42)
Note: R: ring; Cg: the centroid of the ring.
internal standard. IR spectra were recorded with a Mattson 1000 FTIR spectrophotometer
(400–4000 cm−1) in KBr pellets (1% w/w) and are reported in cm−1 units. Microanalyses
were performed using a LECO CHNS-932 C elemental analyzer. Representative 1H, 13C,
19F, and 31P NMR spectra for compounds I and II are found in the online Supplementary
Materials (Figures S1–S8).
A single crystal of 0.5 × 0.40 × 0.40 mm size was selected for X-ray diffraction. Unit-
cell dimensions were obtained using 25 centered reflections on an Enraf-Nonius CAD4
diffractometer25 operating with graphite monochoromated MoKα radiation (λ = 0.71073
Å).
The intensity data were collected in ω = 2θ scan mode within 4.2◦ ≤ 2θ ≤ 46.0◦
for −8 ≤ h ≤ 0, 0 ≤ k ≤ 14, and 0 ≤ l ≤ 31. Out of 2250 unique reflections, 1185 with I >
2σ(I) were used for structure solution and refinement. Data were corrected for Lorenz and
polarization effects. The structure was solved in the orthorhombic space group P212121 by
the combination of direct and Fourier techniques and refined by full-matrix least squares.
All of the nonhydrogen atoms were refined anisotropically. WinGX program package was
used to solve26 and refine the structure (SHELXL97), and ORTEP-3 for Windows27 was
used to draw molecular graphics. Details on data collection and structure refinement for
compound 2 are given in Table 4.
Synthesis of Compounds 1 and 2
Compound 1: 1.00 g (2.50 mmol) of LR was mixed with 0.29 g (4.90 mmol) of freshly
dried (250 ◦C) and finely ground KF in 50 mL of dry acetonitrile at ambient temperature.
After stirring for 10 min, the mixture was refluxed for 1 h. The reaction mixture was cooled,
filtered through a black-band filter paper, and the solvent was evaporated with a rotary
evaporator. The resulting white solid was washed three times with dry diethylether while
etching with a policeman to remove the unreacted ether-solubles and the remaining solid
was dried under vacuum. White powder. Yield: 1.80 mmol, 0.50 g, 71%. M.p. 195–197 ◦C.
IR: ν(cm−1) = 689, 658 (P S)as,s; 737 (P-F); 1593, 1496 (C C); 3010 (C-H)arom. Anal.
Calcd. for C7H7FKOPS2 (260.33): C, 32.3; H, 2.71; S, 24.63; Found: C, 31.95; H, 2.64;
1
S, 24.45%. H NMR (D2O): δ = 3.63 (s, 3H, OCH3), 6.82 (A-part of AAꢁMMꢁX, N =
3
8.7 Hz, 2H, m-H), 7.83 (M-part of AAꢁMMꢁX, JPH = 14.0 Hz (JMX), N = 8.7 Hz, 2H,

SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION
1345
Table 4 Crystal and experimental data for the compound 2
Empirical formula
C31H27FOP2S2
Formula weight
T(K)
560.59
293
Crystal system
Space group (No.)
Colour/shape
a (Å)
Orthorhombic
P 21 21 21 (19)
Colorless/Prism
7.6640(10)
b (Å)
12.991(3)
c (Å)
V (Å3)
28.404(6)
2827.9(9)
Z
4
Radiation
0.71073 (Mo Kα)
0.331
µ (mm−1
)
F(000)
1168
h, k, l range
Crystal size (mm)
−8 ≤ h ≤ 0, 0 ≤ k ≤ 14, 0 ≤ l ≤ 31
0.50 × 0.40 × 0.40
2250
1185
2.1–23.5
No. of reflections collected
No. of independent reflections
θ range for data collection
Data/restraints/parameters
Goodness-of-fit on F2
1185/0/335
1.012
R indices [I>2s(I)]: R1, wR2
R indices (all data): R1, wR2
(
0.066, 0.172
0.175, 0.220
0.503, −0.346
Enraf-Nonius CAD4
Enraf-Nonius CAD4 Express
WinGX (SHELXL and SHELXS)
Full matrix
ρ)max, ( ρ)min eÅ−3
Measurement
Program system
Structure determination
Refinement
CCDC deposit number
828914
1
o-H). 13C{ H} NMR (D2O): δ = 55.7 (s, OCH3), 113.8 (d, 3JPC = 14.0 Hz, C-m), 131.2
2
1
(d, JPC = 14.6 Hz, C-o), 133.5 (dd, JPC = 117.3 Hz, 2JCF = 25.4 Hz, C-i), 161.5 (d,
4JPC = 3.0 Hz, C-p). 31P NMR (D2O): δ = 129.8 (td, 3JPH = 14.8 Hz, 1JPF = 1030.4 Hz).
19F NMR (D2O): δ = −29.4 (d, JPF = 1027.2 Hz). APCI/ESI MS (anion mode); m/z:
1
221.4 calculated for the anion of 1: 221.2, 100%.
Compound 2: 0.50 g (1.20 mmol) of compound 1 was dissolved in 10 mL of water.
To this solution, equivalent volume of 5% aqueous tetraphenylphosphonium chloride was
added dropwise. The precipitation of compound 2 is almost immediate; the salt can be
recrystallized from methanol or water. Colorless crystals. Yield: 1.40 mmol, 0.80 g, 74%.
M.p. 150–151 ◦C. IR: ν(cm−1) = 698, 689 (P S)as,s; 721 (P-F); 1590, 1481 (C C); 3050
(C-H)arom. Anal. Calcd. for C31H27FOP2S2 (560.62): C, 66.41; H, 4.85; S, 11.44; Found:
C, 66.42; H, 4.79; S, 11.51%. 1H NMR (CD3OD): δ = 3.37 (s, 3H, OCH3), 6.85 (A-part
1
of AAꢁMMꢁX, N = 8.8 Hz, 2H, m-H), 7.70–8.02 (m, 22H, o-H, Ph4P+). 13C{ H} NMR
(CD3OD): δ = 54.7 (s, OCH3), 112.5 (d, 3JPC = 15.3 Hz, C-m), 131.4 (d, 2JPC = 14.5 Hz,
C-o), 135.6 (dd, 1JPC = 102.7 Hz, 2JCF = 26.2 Hz, C-i), 161.5 (s, C-p). 31P NMR (CD3OD):
δ = 127.5 (td, 3JPH = 13.8 Hz, 1JPF = 1024.6 Hz), 24.2 (s, Ph4P+). 19F NMR (CD3OD):
δ = −25.9 (d, 1JPF = 1028.3 Hz). APCI/ESI MS (anion mode): m/z: 221.4; Calculated for
the anion of 2: m/z: 221.2; 100%; cation mode: m/z: 339,1; Calculated for the cation of 2:
m/z: 339.4.

˘
E. G. SAGLAM ET AL.
1346
REFERENCES
1. Foreman, M. St. J.; Slawin, A. M. Z.; Woollins, J. D. Heteroat. Chem. 1999, 10, 651-657.
2. Karakus¸, M.; Yılmaz, H.; Bulak, E. Rus. J. Coord. Chem. 2005, 31, 316-321.
3. Van Zyl, W. E. Comments Inorg. Chem. 2010, 31, 13-45.
4. Aragoni, M. C.; Arca, M.; Demartin, F.; Devillanova, F. A.; Graiff, C.; Isaia, F.; Lippolis, V.;
Tiripicchio, A.; Verani, G. Eur. J. Inorg. Chem. 2000, 2239-2244.
5. Przychodzen, W.; Chojnacki, J. Heteroat. Chem. 2008, 19, 271-282.
6. Diemert, K.; Kuchen, W. Phosphorus, Sulfur Silicon Relat. Elem. 1977, 3, 131-136.
7. Hoffmann, H.; Schumacher, G. Tetrahedron Lett. 1967, 31, 2963-2966.
8. Chavdarian, C. G. US Patent 4483225, 1987.
9. Bara, A. C.; Silvestru, C.; Haiduc, I. Anticancer Res. 1991, 11, 1651-1656.
10. Du¨rckheimer, W.; Bormann, D.; Ehlers, E.; Schrinner, E.; Heymes, R. U.S. Patent 5710146,
1998.
11. Klaehn, J. R.; Harrup, M. S.; Law, J. D.; Peterman, D. R. US Patent 7704468 B1, 2010.
12. Klaehn, J. R.; Peterman, D. R.; Harrup, M. S.; Tillotson, R.; Luther, T. A.; Law, J. D.; Daniels,
L. M. Inorg. Chim. Acta 2008, 361, 2522-2532.
13. Roesky, H. W. Chem. Ber. 1968, 101, 3679-3687.
14. Roesky, H. W. Angew. Chem. Int. Ed. 1968, 7, 814-815.
15. Cavell, R. G.; Doty, L. F. Inorg. Chem. 1978, 17, 3086-3093.
16. Leavitt, C. M.; Gresham, G. L.; Benson, M. T.; Gaumet, J. J.; Peterman, D. R.; Klaehn, J. R.;
Moser, M.; Aubriet, F.; Stipdonk, M. J. V.; Groenewold, G. S. Inorg. Chem. 2008, 47, 3056-3064.
17. Tworowska, I.; Dabkowski, W. Chem. Commun. 1998, 2611-2612.
18. Emsley, J.; Hall, D. The Chemistry of Phosphorus; London: Harper & Row Publishers: 1976; p.
87.
19. Roesky, H. W. Z. Naturforsch. 1967, 22b, 716-718.
20. Roesky, H. W.; Tebbe, F. N.; Muetterties, E. L. Inorg. Chem. 1970, 9, 831-836.
21. Silverstein, R. M.; Webster, F. X.; Kiemle, D. J. Spectrometric Identification of Organic Com-
pounds, Vol. 4, 7th ed.; Hoboken, NJ: Wiley: 2005; pp. 204-245.
22. Klaehn, J. R.; Peterman, D. R.; Harrup, M. S.; Luther, T. A.; Daniels, L. M. Inorg. Chim. Acta
2011, 370, 519-522.
23. Sag˘lam, E. G.; C¸ elik, O.; Yılmaz, H.; Ide, S. Transition Met. Chem. 2010, 35, 399-405.
24. Cremer, D.; Pople, J. A. J. Am.Chem. Soc. 1975, 97, 1354-1358.
25. Enraf-Nonius, D. CAD4 Express Software; Enraf-Nonius, Delft: The Netherlands, 1994.
26. Sheldrick, G. M. Acta Crystallogr., Sect. A: Found Crystallogr. 2008, 64, 112-122.
27. Farrugia, L. J. Appl. Crystallogr. 1997, 30, 565-566.