Reaction of perfluoroalkyl Grignard reagents with phosphorus trihalides: A new route to perfluoroalkyl-phosphonous and-phosphonic acids

Article abstract of DOI:10.1021/ic102063e

The reaction of perfluoroalkyl Grignard reagents with phosphorus(III) halides was explored. In the process a new convenient, one-pot, high yield method for the synthesis of (perfluoroalkyl)phosphonic acids has been developed. Perfluoroalkyl Grignard reagents react with phosphorus trichloride or phosphorus tribromide to form (perfluoroalkyl)phosphonous dihalides. Hydrolysis gives the corresponding (perfluoroalkyl)phosphonous acids. Oxidation of the phosphonous acids with H₂O₂ produces (perfluoroalkyl) phosphonic acids in 60-78% overall yields, based on the corresponding perfluoroalkyl iodide. The X-ray crystal structures of the toluidinium salts, [MeC₆H₄NH₃]₂[C₂F ₅PO₃] and [MeC₆H₄NH ₃][C₈F₁₇P(O)₂OH], are reported.

Full text of DOI:10.1021/ic102063e

1484 Inorg. Chem. 2011, 50, 1484–1490
DOI: 10.1021/ic102063e
Reaction of Perfluoroalkyl Grignard Reagents with Phosphorus Trihalides:
A New Route to Perfluoroalkyl-phosphonous and -phosphonic Acids
Adil I. Hosein,† Xavier F. Le Goff,‡ Louis Ricard,‡ and Andrew J. M. Caffyn*,†,§
†Department of Chemistry, The University of the West Indies, St. Augustine, Trinidad & Tobago,
‡
ꢀ ꢀ ꢀ ꢀ
Laboratorie “Heteroelements et Coordination”, Ecole Polytechnique, CNRS UMR 7653, 91128 Palaiseau
ꢀ
§
Cedex, France, and School of Biology, Chemistry & Health Science, Manchester Metropolitan University,
John Dalton Building, Chester St., Manchester M1 5GD, U. K.
Received October 12, 2010
The reaction of perfluoroalkyl Grignard reagents with phosphorus(III) halides was explored. In the process a new
convenient, one-pot, high yield method for the synthesis of (perfluoroalkyl)phosphonic acids has been developed.
Perfluoroalkyl Grignard reagents react with phosphorus trichloride or phosphorus tribromide to form (perfluoroalkyl)-
phosphonous dihalides. Hydrolysis gives the corresponding (perfluoroalkyl)phosphonous acids. Oxidation of the
phosphonous acids with H2O2 produces (perfluoroalkyl)phosphonic acids in 60-78% overall yields, based on the
corresponding perfluoroalkyl iodide. The X-ray crystal structures of the toluidinium salts, [MeC6H4NH3]2[C2F5PO3] and
[MeC6H4NH3][C8F17P(O)2OH], are reported.
ꢀ
Introduction
(perfluoroalkyl)phosphonic acids. Emeleus and co-workers
seminal discovery that white phosphorus reacts with triflu-
oromethyl iodide in an autoclave, to provide a mixture of
trifluoromethyl-substituted phosphorus(III) compounds
opened up the chemistry of perfluoroalkylphosphorus com-
pounds (Scheme 1).8-10 The simplest perfluoroalkylphospho-
nic acid CF3P(O)(OH)2 was thus synthesized by oxidative
hydrolysis of CF3PX2, (CF3)2PX, (X = Cl, I), P(CF3)3, or
CF3PH2, compounds which in turn were synthesized, directly
or indirectly, from the phosphorus/CF3I reaction.10,11
The higher analogues of perfluoroalkylphosphonic acids
have been synthesized using similar methodology.12,13 For
(Perfluoroalkyl)phosphonic acids have proved to be of
interest in several diverse applications including use as anti-
foaming agents,1 as alumina HPLC stationary phases,2 as
sublimation-type thermal transfer sheets,3 as ligand compo-
nents for optical gain media,4 as etchants of transparent
In-Sn oxide electrode films,5 as fluorinated ion-exchange
membranes in fuel cells6 and recently as lubricants for micro/
nano-optoelectromechanical systems.7 Despite this interest,
(perfluoroalkyl)phosphonic acids(and indeedother perfluor-
oalkyl-substituted phosphorus compounds) have histori-
cally proved difficult to make. Generally, modifications
of the original procedure are still used for the synthesis of
example, Shreeve and Mahmood reported the synthesis of
14
ꢀ
C2F5P(O)(OH)2 by the Emeleus method (Scheme 2). The
major problems with this methodology stem from the initial
*To whom correspondence should be addressed. Phone: þ44 (0)161 2471443.
E-mail: a.caffyn@mmu.ac.uk..
(1) Heid, C.; Hoffmann, D.; Polster, J. Ger. Offen. 2,233,941, 1974.
(2) Haky, J. E.; Blauvelt, T. M.; Wieserman, L. F. J. Liquid Chromatogr.
Relat. Technol. 1996, 19, 307–332.
ꢀ
Emeleus method. While the final oxidation and hydrolysis
ꢀ
steps proceed in high yield, the initial Emeleus procedure
does not. Initial conversions are often modest and thus un-
reacted perfluoroalkyl iodide needs to be recovered and recycled
for optimum efficiency. Separation of the light-sensitive
(3) Mori, M.; Sakurai, O. Jpn. Kokai Tokkyo Koho 6199061, 1994.
(4) Mohajer, Y.; Panackal, A.; Sharma, J.; Hsiao, Y.-L.; Mininni, R.;
Thomas, B.; Zhu, J. PCT Int. Appl. 018592, 2003. Araki, T.; Tanaka, Y.; Andou,
Y.; Komatsu, Y. PCT Int. Appl. 091343, 2003.
(5) Saito, Y.; Horiuchi, Y. PCT Int. Appl. 081658, 2003.
ꢀ
(8) Bennett, F. W.; Brandt, G. R. A.; Emeleus, H. J.; Haszeldine, R. N.
(6) Bhamidipati, M.; Lazaro, E.; Lyons, F.; Morris, R. S. Mater. Res. Soc.
Symp. Proc. 1998, 496, 217–222. Yoshitake, M.; Kunisa, Y.; Yoshida, N. Jpn.
Kokai Tokkyo Koho 11339824, 1999. Yoshitake, M.; Yoshida, N.; Kunisa, Y.;
Shimodaira, S. Jpn. Kokai Tokkyo Koho 11135135, 1999. Yoshitake, M.; Endo,
E.; Kunisa, Y. Jpn. Kokai Tokkyo Koho 11307108, 1999. Yoshitake, M.;
Yoshida, N.; Kokusa, Y.; Shimodaira, S. Jpn. Kokai Tokkyo Koho 11135136,
1999. Kimoto, K. PCT Int. Appl. 063991, 2000. Li, S.; Zhou, Z.; Liu, M.; Li, W.
PCT Int. Appl. 072413, 2005. Motomura, A.; Tayanagi, J.; Saito, M.; Endo, E.
Jpn. Kokai Tokkyo Koho 012520, 2007.
Nature 1950, 166, 225.
ꢀ
(9) Bennett, F. W.; Emeleus, H. J.; Haszeldine, R. N. J. Chem. Soc. 1953,
1565–1571.
ꢀ
(10) Bennett, F. W.; Emeleus, H. J.; Haszeldine, R. N. J. Chem. Soc. 1954,
3598–3603.
ꢀ
(11) Bennett, F. W.; Emeleus, H. J.; Haszeldine, R. N. J. Chem. Soc. 1954,
3896–3904.
ꢀ
(12) Emeleus, H. J.; Smith, J. D.. J. Chem. Soc. 1959, 375–381.
(13) Brecht, H. Ger. Offen. 2,110,769, 1972. Brecht, H.; Hoffmann, D. Ger.
Offen. 2,110,767, 1972.
(14) Mahmood, T.; Shreeve, J. M. Inorg. Chem. 1986, 25, 3128–3131.
(7) Bhushan, B.; Cichomski, M.; Hoque, E.; DeRose, J. A.; Hoffmann, P.;
Mathieu, H. J. Microsyst. Technol. 2006, 12, 588–596.
r
pubs.acs.org/IC
Published on Web 01/12/2011
2011 American Chemical Society

Article
Inorganic Chemistry, Vol. 50, No. 4, 2011 1485
Scheme 1
The main reason that perfluoroalkyl phosphorus deriva-
tives have proved more difficult to make than their corre-
sponding alkyl derivatives is a relative lack of effective
perfluoroalkyl carbanion organometallic reagents. It is
well-known that perfluoroalkyl derivatives (particularly
trifluoromethyl) of the more electropositive metals are ther-
mally unstable.20-22 Although perfluoroalkyl derivatives of
less electropositive metals exhibit better thermal stability,
they tend to be markedly less nucleophilic than their alkyl
counterparts. Thus, to date, attempts to synthesize (perfluoro-
alkyl)phosphorus compounds from the reactions of main
group perfluoroalkyl organometallics with phosphorus tri-
halides have met with mixed success. Reaction of pentafluor-
oethyl lithium with phosphorus trichloride at low tem-
perature gave P(C2F5)3 in 41% yield.23 Caution must be
exercised, however, as the authors have warned of the risk of
explosive decomposition in closely related procedures.24 Less
nucleophilic bis(trifluoromethyl) cadmium, mercury and tell-
urium reagents25 have produced small to moderate yields of
P(CF3)3, the latter two under forcing conditions. Interest-
ingly the reactivity of perfluoroalkyl Grignards with PX3 (X =
Cl, Br) does not appear to have been previously investigated.
This is despite the fact that Grignard treatment of PCl3 has
been studied for over a century26 and is established as the
preferred method for the synthesis of trialkyl and many
triarylphosphines.27-30 This therefore was the subject of
our study reported here. In the course of our investigation
we have developed a convenient, atom efficient, one-pot
synthesis of (perfluoroalkyl)phosphonic and (perfluoroalkyl)-
phosphonous acids in 60-78% overall yields.
Scheme 2
perfluoroalkylphosphonous diiodides from the bis(perfluoro-
alkyl)phosphinous iodides, phosphorus triiodide, perfluor-
oalkyliodides, and other materials is required. This results in
reduced yields and can be problematic (for example, co-
distillation of C4F9PI2/(C4F9)2PI as well as C6F13PI2/
(C6F13)2PI is a particular problem).13 In addition, direct
hydrolysis of the isolated iodides results in trace iodine con-
tamination. This issue can be circumvented on a small scale by
metathesis of the iodides to chlorides; however, stoichiometric
AgCl or SbCl3 are required.14,15 Ultimately these methods lead
to maximum overall yields of the final perfluoroalkylpho-
sphonic acid of 30% or less based on the corresponding per-
fluoroalkyl iodide.
Reaction of Perfluoroalkyl Grignard Reagents with PCl3
and PBr3
Equimolar amounts of C2F5MgCl (generated in situ from
C2F5I and C2H5MgCl in ether)31 and PCl3 were reacted
at -78 °C in ether solution for 6 h. After warming to room
temperature, a triplet of quartets was observed in the 31P
NMR spectrum, at δ 142.4, indicating formation of C2F5PCl2
(lit.14 δ 141.7). This was confirmed by the observation of
Recently, progress has been made in the development of
improved syntheses of other perfluoroalkyl substituted phos-
phorus compounds. For example, tris(perfluoroalkyl)difluoro-
phosphoranes, (Rf)3PF2 (Rf = CnF2nþ1), have been made
from trialkylphosphines via either electrochemical fluorina-
tion in anhydrous HF,16 or direct fluorination with F2.17
Tris(perfluoroalkyl)phosphines, P(Rf)3, are produced by the
fluoride mediated reaction of Me3SiRf with P(OR)3 (R = Ph,
p-C6H4CN),18 and metathesis procedures have been used for
the synthesis of perfluoroalkyl substituted aryl- and alkyl-
phosphines.19 In the case of (Rf)3PF2 and P(Rf)3, alkaline
hydrolysis generates the corresponding perfluoroalkylpho-
sphonic acids.16 This synthetic strategy, however, is not
“atom efficient” with respect to perfluoroalkyl groups.
doublets at δ -80.0 (3JPF = 15 Hz) and δ -123.8 (2JPF
68 Hz) in the 19F NMR spectrum [lit.14 δ -78.5 (3JPF
=
=
14.65 Hz), -122.5 (2JPF = 68.36 Hz)]. Quenching of the
mixture with water led to formation of crude phosphonous
1
acid C2F5PH(O)OH [31P NMR δ 7.4 (dt, JPH = 588 Hz,
(20) Burton, D. J.; Yang, Z.-Y. Tetrahedron 1992, 48, 189–275.
(21) Haszeldine, R. N. Nature 1951, 167, 139–140.
ꢁ
ꢁ
ꢀ
ꢀ
(22) Kvı
´
cala, Stambasky, J. J.; Skalicky, M.; Paleta, O. J. Fluorine Chem.
2005, 126, 1390–1395.
(23) Peters, R. G.; Bennett, B. L.; Schnabel, R. C.; Roddick, D. M. Inorg.
Chem. 1997, 36, 5962–5965.
(15) Maslennikov, I. G.; Laurent’ev, A. N.; Khovanskaya, N. V.; Lebedev,
V. B.; Sochilin, E. G. J. Gen. Chem. USSR 1979, 49, 1307–1309.
(16) Yagupol’skii, L. M.; Semenii, V. Ya.; Zavatskii, V. N.; Bil’dinov,
K. N.; Kirsanov, A. V. J. Gen. Chem. USSR 1984, 54, 692–695. Kovaleva,
T. V.; Martynyukh, E. G.; Semenii, V. Ya. J. Gen. Chem. USSR 1989, 59, 2245–
2248. Ignat'ev, N.; Sartori, P. J. Fluorine Chem. 2000, 103, 57–61.
(17) Kampa, J. J.; Nail, J. W.; Lagow, R. J. Angew. Chem., Int. Ed. Engl.
1995, 34, 1241–1244.
(24) Roddick, D. M. Chem. Eng. News 1997, 75(40), 6.
(25) Krause, L. J.; Morrison, J. A. J. Am. Chem. Soc. 1981, 103, 2995–
3001. Ganja, E. A.; Ontiveros, C. D.; Morrison, J. A. Inorg. Chem. 1988, 27,
4535–4538. Ganja, E. A.; Morrison, J. A. Inorg. Chem. 1990, 29, 33–38.
(26) Auger, V.; Billy, B. C. R. 1904, 139, 597–599.
(27) Hibbert, H. Ber. 1906, 39, 160–162.
(28) Kharasch, M. S.; Reinmuth, O. Grignard Reactions of Nonmetallic
Substances; Constable & Co. Ltd.: London, U.K., 1954.
(29) Silverman, G. S. Nucleophilic Substitution with Electrophilic Or-
ganic, Main Group and Transition Metal Species. In Handbook of Grignard
Reagents; Silverman, G. S., Rakita, P. E., Eds.; Marcel Dekker Inc.: New York,
1996; pp 307-354.
(18) Murphy-Jolly, M. B.; Lewis, L. C.; Caffyn, A. J. M. Chem. Commun.
2005, 4479–4480.
€
(19) Hoge, B.; Thosen, C. Inorg. Chem. 2001, 40, 3113–3116. Vaillard,
S. E.; Postigo, A.; Rossi, R. A. Organometallics 2004, 23, 3003–3007.
Eisenberger, P.; Kieltsch, I.; Armanino, N.; Togni, A. Chem. Commun. 2008,
1575–1577. Brisdon, A. K.; Herbert, C. J. Chem. Commun. 2009, 6658–6660.
Lewis-Alleyne, L. C.; Murphy-Jolly, M. B.; Le Goff, X. F.; Caffyn, A. J. M.
Dalton Trans. 2010, 39, 1198–1200. Lanteri, M. N.; Rossi, R. A.; Martin, S. E.
J. Organomet. Chem. 2009, 694, 3425–3430. Phelps, J. E.; Frawley, S. B.; Peters,
R. G. Heteroat. Chem. 2009, 20, 393–397.
(30) Quin, L. D. A Guide to Organophosphorus Chemistry; Wiley-Inter-
science: New York, 2000.
(31) McBee, E. T.; Roberts, C. W.; Meiners, A. F. J. Am. Chem. Soc.
1957, 79, 335–337. Denson, D. D.; Smith, C. F.; Tamborski, C. J. Fluorine Chem.
1973/74, 3, 247–258.

1486 Inorganic Chemistry, Vol. 50, No. 4, 2011
Hosein et al.
Scheme 3
2JPF = 80 Hz); 19F NMR δ -81.1 (s, CF3), -132.0 (d, CF2)].
Oxidation of the solution with aqueous 35% H2O2 produced
the crude phosphonic acid C2F5P(O)(OH)2 (Scheme 3).
It was subsequently found that use of PBr3 in place of PCl3
and the bromo-Grignard, C2F5MgBr, instead of the chloro-
Grignard, C2F5MgCl, led to a cleaner reaction and slightly
increased yields of these acids. Thus, reaction at -78 °C of
equimolar amounts of C2F5MgBr (generated fromC2F5I and
C2F5MgBr),31 and PBr3 led to the formation of a species
tentatively proposed to be C2F5PBr2. This assignment was
based on the observation of a triplet of quartets at δ 128.1 in
the 31P NMR spectrum, and the observation of doublets at
δ -79.2 (3JPF = 18 Hz) and δ -117.7 (2JPF = 53 Hz) in the
19F NMR spectrum of the mixture. No attempt was made to
isolate C2F5PBr2. Oxidative quenching with 35% H2O2 led to
crude C2F5P(O)(OH)2 as before. Other species present are
magnesium salts, C2H5I and small amounts of H3PO4 origi-
nating from unreacted PBr3. The H3PO4 was removed from
the aqueous mixture by addition of ammonia, which resulted
in the precipitation of NH4MgPO4. After filtration, treat-
ment with Amberlyst (IR 120) cation exchange resin in the
Scheme 4
(R = H, Me). In the case of Rf = C6F13, for example,
evaporation of solvent and recrysallization from dichloro-
methane/methanol gave crystalline [C6H5NH3][C6F13PH(O)2]
in 70% yield based on C6F13I. As far as we are aware, with the
exception of Rf = CF3, perfluoroalkylphosphonous acids
and their salts have not been isolated before. Attempts to
thermally decompose solutions of [C6H5NH3][C6F13PH(O)2]
were successful, [C6H5NH3][H2PO3] and 1H-perfluorohex-
ane being produced quantitatively. Oxidation of the phos-
phonous acid in situ, as before gives the corresponding
phosphonic acid derivatives.
During reactions using a slight excess of C2F5MgCl with
PCl3, in addition to the C2F5PCl2 resonance, a faint multiplet
at δ 61.3 in the 31P NMR spectrum of the reaction mixture
was observed. In the 19F NMR spectrum doublets at δ -82.0
(3JPF = 15 Hz) and δ -117.5 (2JPF = 60 Hz) were observed.
Hþ form removed remaining NH4 and Mg2þ ions. The
þ
This suggested formation of traces of (C2F5)2PCl [lit:14 31
P
phosphonic acid could then be conveniently isolated by ether
extraction, followed by addition of two equivalents of
p-toluidine. This resulted in selective precipitation of the
corresponding bis(p-toluidinium) salt, [MeC6H4NH3]2-
[C2F5PO3] in 60% overall yield based on C2F5I. In an
analogous manner, using C4F9MgBr, the perfluorobutyl-
substituted phosphonic acid salt, [MeC6H4NH3]2[C4F9PO3]
could be isolated in 60% yield. Quantitative isolation of the
corresponding pure phosphonic acid, C4F9P(O)(OH)2, could
be achieved by eluting an aqueous Na2CO3 solution of
[MeC6H4NH3]2[C4F9PO3] through the Hþ form of the cation
exchange resin. Using RfMgBr (Rf = C6F13, C8F17), the
corresponding longer chain (perfluoroalkyl)phosphonic
acids could be made. In the case of these longer chain acids,
however, after treatment of ether solutions of the crude acids
with p-toluidine, the mono-p-toluidinium salts crystallized,
thus for example, [MeC6H4NH3][C6F13P(O)2OH] was iso-
lated as white crystals in 78% overall yield based on C6F13I.
The intermediate free phosphonous acid, C2F5PH(O)OH,
decomposed on attempted distillation. Addition of aniline or
p-toluidine to the reaction mixture led to the formation of
intractable oils. Since the parent free acid, CF3PH(O)OH has
proved thermally sensitive, and difficult to obtain in analy-
tically pure form,10,11,32 no further attempts were made to
isolate the pure acid. For the longer chain perfluoroalkyl
derivates, however, it was found that after washing the
residual reaction mixture with water, the intermediate phos-
phonous acids can be precipitated from the organic layer as
anilinium or p-toluidinium salts by addition of RC6H4NH2
NMR; δ 61.17; 19F NMR δ -81.63 (d, 3JPF = 14.56 Hz) and
2
δ -117.2 (d, JPF = 58.59 Hz)], but upon work up no
(C2F5)2P(O)OH was isolated. Subsequent optimization,
using a 6 fold excess of C2F5MgBr and longer reaction time
at -64 °C (9 h), led to observation of a 3:1 ratioof (C2F5)2PCl
to C2F5PCl2 (Scheme 4). Oxidative hydrolysis with 35%
H2O2 allowed isolation bis(perfluoroethyl)phosphinic acid,
(C2F5)2P(O)OH in 11% yield based on C2F5I.
No evidence of formation of tris(perfluoroalkyl)phos-
phines was observed. It appears that substitution of a third
perfluoroalkyl group is so slow at reduced temperature that
perfluoroalkyl Grignard decomposition sets in before it can
occur. It is well established that perfluoroalkyl Grignard
reagents must be prepared and used at low temperature.
Above -20 °C, decomposition is rapid in ether (and even
faster in other solvents), to give the reduced perfluoroalkane,
RfH, or a fluoroolefin via β-elimination.33,34
Attempts to react iC3F7MgBr35 with PBr3 lead to predo-
minantly unreacted PBr3, even after 12 h at -78 °C. 31P
NMR monitoring of the reaction mixture indicated a trace of
a species, tentatively assigned as iC3F7PBr2 on the basis of a
doublet of septets at δ 131 (2JPF = 80, 3JPF = 17 Hz). Upon
workup, however, no perfluoroisopropyl-phosphonous or
-phosphonic acid could be recovered. It should be further
noted that this method cannot be extended to the synthesis of
(33) Haszeldine, R. N. J. Chem. Soc. 1952, 3423–3428. Howells, R. D.;
Gilman, H. J. Fluorine Chem. 1975, 5, 99–114. Thoai, N. J. Fluorine Chem.
1975, 5, 115–125.
(34) Smith, C. F.; Soloski, E. J.; Tamborski, C. J. Fluorine Chem. 1974, 4,
35–45.
(32) Burg, A. B.; Griffiths, J. E. J. Am. Chem. Soc. 1961, 83, 4333–4337.
Harris, G. S. J. Chem. Soc. 1958, 512–519.
(35) Chambers, R. D.; Musgrave, W. K. R.; Savory, J. J. Chem. Soc. 1962,
1993–1999.

Article
Inorganic Chemistry, Vol. 50, No. 4, 2011 1487
Figure 1. Molecular structure of [MeC6H4NH3]2[C2F5PO3]. Ellipsoids drawn at 50% probability.
the trifluoromethyl-substituted phosphorus acids, since
CF3MgBr is thermally unstable and known to decompose
below -78 °C.20-22,36
To help establish the scope of the reactivity of perfluor-
oalkyl Grignard reagents toward basic phosphorus reagents,
treatment with phosphorus(III) iodide was examined. No
reaction was observed, however, between PI3 and C2F5MgBr
after 12 h at -78 °C. The low solubility of PI3 in ether (the
preferred solvent for the formation and use of perfluoroalkyl
Grignard reagents)20,34 may explain this lack of reactivity.
The reaction of conventional alkyl and aryl Grignard
reagents with triphenylphosphite in refluxing ether has been
established as an alternative route to tertiary phosphines.37 In
light of this procedure, we also tested the low temperature
treatment of the perfluoroalkyl Grignard, C4F9MgBr, with
triphenylphosphite in ether. After 6 h at -78 °C, however, no
substitution of perfluoroalkyl groups on to phosphorus was
detected by 31P and 19F NMR. Thermal decomposition of
C4F9MgBr was observed upon warming to room temperature.
Figure 2. Molecular structure of [MeC6H4NH3][C8F17P(O)2OH]. Ellip-
soids are drawn at 50% probability.
X-ray Structure of the Perfluoroalkylphosphonates,
[MeC6H4NH3]2[C2F5PO3] and [MeC6H4NH3][C8F17P-
(O)2OH]
Although thestructure of a trifluoromethyl-susbtitutedphos-
phonate has been determined,42 no phosphonates substituted
with a longer perfluoroalkyl chain have yet been described.
We report here the first crystal and molecular structures of
extended chain perfluoroalkyl phosphonates.
Alkyl phosphonate salts are of interest because of their
potential utility as sorbents, catalysts and because of the ease
with which layered, pillared and intercalated structures can
be obtained.38 Structures of extended alkyl chain phospho-
nates have thus been intensely studied recently.39,40 Shreeve
et al., in reporting the first crystal structures of bis(n-per-
fluoroalkyl)phosphinic acids, noted that in general it is difficult
to crystallize compounds having long perfluoroalkyl chains.41
[MeC6H4NH3]2[C2F5PO3] was crystallized from metha-
nol, the molecular structure is shown in Figure 1. The
phosphorus configuration is approximately tetrahedral. Each
of the phosphonate oxygens are hydrogen bonded to two
different p-toluidinium cations. Each p-toluidinium cation is
hydrogen bonded to three phosphonate dianions. All three
P-O bond distances are similar (1.507(1), 1.510(1) and
1.513(1) A). The average O-P-O bond angle is 114.3° and
the P-C bond length is 1.868(1) A. It has previously been
noted that the structures of bis(perfluoroalkyl)phosphinates
exhibit longer P-C bonds, shorter P-O bonds and more
obtuseO-P-O anglesthan found for dialkylphosphinates.41
Comparison of structural data of [MeC6H4NH3]2[C2F5PO3]
with that reported for n-alkylphosphonates,39,40 suggests that
these same trends seem to also apply to perfluoroalkylpho-
sphonates, albeit that the differences are relatively subtle.
[MeC6H4NH3][C8F17P(O)2OH] was crystallized from
chloroform/acetone (9:1). The molecular structure is shown
in Figure 2. The hydrogenphosphonate groups are situated
adjacent to the p-toluidinium ions forming neutral sheets
(36) Haszeldine, R. N. J. Chem. Soc. 1954, 1273–1279. McBee, E. T.;
Battershell, R. D.; Braendlin, H. P. J. Org. Chem. 1963, 28, 1131–1133.
(37) Gilman, H.; Vernon, C. C. J. Am. Chem. Soc. 1926, 48, 1063–1066.
(38) Cao, G.;Hong, H.-G.;Mallouk, T. E. Acc. Chem. Res. 1992, 25, 420–427.
(39) Bauer, E. M.; Bellitto, C.; Colapietro, M.; Ibrahim, S. A.; Mahmoud,
M. R.; Portalone, G.; Righini, G. J. Solid State Chem. 2006, 179, 389–397.
Bujoli, B.; Pena, O.; Palvadeau, P.; Le Bideau, J.; Payen, C.; Rouxel, J. Chem.
Mater. 1993, 5, 583–587. Bellitto, C.; Bauer, E. M.; Leone, P.; Meerschaut, A.;
Guillot-Deudon, C.; Righini, G. J. Solid State Chem. 2006, 179, 579–589. Le
Bideau, J.; Bujoli, B.; Jouanneaux, A.; Payen, C.; Palvadeau, P.; Rouxel, J. Inorg.
Chem. 1993, 32, 4617–4620. Adair, B. A.; Neeraj, S.; Cheetham, A. K. Chem.
Mater. 2003, 15, 1518–1529. Khan, M. I.; Lee, Y.-S.; O'Connor, C. J.; Haushalter,
R. C.; Zubieta, J. Chem. Mater. 1994, 6, 721–723. Harrison, W. T. A.; Dussack,
L. L.; Jacobsen, A. J. Acta Crystallogr., Sect C 1997, 53, 200–202. Langley, S.;
Helliwell, M.; Sessoli, R.; Teat, S. J.; Winpenny, R. E. P. Inorg. Chem. 2008, 47,
497–507.
(40) Cao, G.; Lynch, V. M.; Swinnea, J. S.; Mallouk, T. E. Inorg. Chem.
1990, 29, 2112–2117. Yuge, T.; Kai, N.; Hisaki, I.; Miyata, M.; Norimitsu, T.
Chem. Lett. 2007, 36, 1390–1391. Driss, H.; Boubekeur, K.; Debbabi, M.;
Thouvenot, R. Eur. J. Inorg. Chem. 2008, 3678–3686.
(41) Singh, R. P.; Twamley, B.; Shreeve, J. M. J. Chem. Soc., Dalton
Trans. 2000, 4089–4092.
€
(42) Pantenburg, I.; Thosen, C.; Hoge, B. Z. Anorg. Allg. Chem. 2002,
628, 1785–1788.

1488 Inorganic Chemistry, Vol. 50, No. 4, 2011
Hosein et al.
Figure 3. Unit cell packing of [MeC6H4NH3][C8F17P(O)2OH]. Ellipsoids are drawn at 50% probability.
(Figure 3). The perfluorooctyl groups point away from this
plane. As has been observed for other hydrogenphos-
phonates,40,42 there is a large difference in phosphorus-
oxygen bond distances; the P-OH distance (1.553(1) A)
being considerably longer than the two other P-O distances
(1.486(1) and 1.498(1) A). The hydrogenphosphonate OH’s are
hydrogen bonded, to a phosphonate oxygen of an adjacent
hydrogenphosphonate group in a pairwise fashion forming
an eight membered ring (such eight membered rings have been
observed in the structures of other hydrogenphosphonate
salts).42 This phosphonate oxygenis also hydrogen bonded to
a p-toluidinium cation, with the remaining phosphonate
oxygen hydrogen bonded to two p-toluidinium cations.
reaction to monosubstitution.43 Thus the Grignard method is
not generally applicable tothe synthesis of alkylphosphonous
dihalides except in cases where sterically bulky phosphonous
dihalides are targeted and thus where overalkylation
is avoided.44 Another reaction, where selective mono-, di-
and trisubstitution are possible, is the dropwise addition
of C6F5MgBr to PCl3.45
The specific production of (perfluoroalkyl)phosphonous
dihalides from perfluoroalkyl Grignard treatment of phos-
phorus trihalides means that a selective and convenient new
route to (perfluoroalkyl)phosphonous and (perfluoroalkyl)-
phosphonic acids has been established through aqueous
quenching or oxidation with aqueous H2O2 respectively.
Experimental Section
Conclusion
General Experimental Procedures. Perfluoroalkyliodides
CnF2nþ1I (n = 2, 4, 6, 8) were purchased from Apollo
Scientific. PCl3, PBr3, P(OPh)3, aniline, and p-toluidine were
purchased from Sigma-Aldrich and used as received. C2H5MgBr
and C2H5MgCl were prepared in ether and standardized by
literature methods. All organic solvents used were distilled
and degassed. Ether was dried and distilled from sodium/
benzophenone and stored over 4 A molecular sieves. Reactions
were carried out in Schlenk tubes and under an inert atmo-
sphere of dry argon using standard Schlenk line techniques.
In this study we have shown that when PCl3 or PBr3 are
reacted stoichiometrically with perfluoroalkyl Grignards,
(perfluoroalkyl)phosphonous dihalides are formed exclu-
sively. By contrast, although a few alkylphosphonous diha-
lides have been prepared by replacement of one halide of PX3
by reaction with a Grignard reagent, the simplest and com-
monest conventional alkyl or aryl Grignards are generally too
reactive for this purpose and give high yields of trialkyl- or
triaryl-phosphines. This method is therefore widely used for
the synthesis of trialkylphosphines and triarylphosphines. It
has been described as “difficult or impossible” to limit the
(44) Voskuil, W.; Arens, J. F. Recl. Trav. Chim. Pays-Bas 1963, 82,
302–304.
(45) Wall, L. A.; Donadio, R. E.; Pummer, W. J. J. Am. Chem. Soc. 1960,
82, 4846–4848. Magnelli, D.; Tesi, G.; Lowe, J., Jr.; McQuistion, W. Inorg.
Chem. 1966, 5, 457–461.
(43) Engel, R.; Cohen, J. I. Synthesis of Carbon-Phosphorus Bonds, 2nd
ed.; CRC Press: Boca Raton, FL, 2004.

Article
Inorganic Chemistry, Vol. 50, No. 4, 2011 1489
31P, 19F, 13C, and 1H NMR spectra were recorded by an
Avance Bruker 400 MHz FT NMR spectrometer with 85%
H3PO4, CCl3F, and Si(CH3)4 as external references, respec-
tively. Elemental analyses were performed by Medac Ltd..
Yields are based on perfluoroalkyl iodides unless otherwise
stated.
Synthesis of [RC6H4NH3][n-C6F13PH(O)2] (R = H, Me).
C6F13I (4.13 g, 9.25 mmol) and C2H5MgBr (9.25 mmol in 35
mL of ether) were reacted while stirring at -78 °C in a 100 mL
Schlenk tube under argon. The Grignard exchange reaction was
allowed to proceed for 1 h after which PBr3 (2.42 g, 8.95 mmol)
was added dropwise to the cold Grignard mixture. After the
addition was complete, the reaction mixture was allowed to stir
at -78 °C for 6 h and then warmed to room temperature over
1 h. The mixture was then cooled to 0 °C, and 25 mL water was
added dropwise while stirring. The mixture was washed with
water (3 ꢀ 100 mL), and RC6H4NH2 (R = H, Me), (10 mmol),
in 50 mL of ether was added dropwise to the washed ether
solution. The ether was evaporated to leave behind a yellowish
residue. The residue was then washed with hot CHCl3 followed
by recrystallization from chloroform/acetone (9:1) to obtain
fine, sticky, white crystals of [RC6H4NH3][n-C6F13PH(O)2].
[C6H5NH3][n-C6F13PH(O)2] (3.0 g, 70%): 31P NMR (dmso-d6):
δ 2.3 (dt, 1JPH = 549 Hz, 2JPF = 72 Hz). 19F NMR (dmso-d6):
δ -79.7 (s, 3F, CF3); -121.9 (br s, 4F, 2 ꢀ CF2), - 122.0 (s, 2F,
(dmso-d6): δ 10.1 (s, br, 3H, ArNH3þ), 7.29 (m, 5H, Ar), 6.9
(d, 1H, P-H). [p-MeC6H4NH3][n-C6F13PH(O)2] (2.6 g, 59%):
31P NMR (dmso-d6): δ 1.7 (dt, 1JPH = 542 Hz, 2JPF = 71.2 Hz).
19F NMR (dmso-d6): δ -80.9 (s, 3F, CF3, 3F), -122.2 (br s, 2 ꢀ
CF2, 4F), -122.3 (s, CF2, 2F), -126.4 (s, CF2, 2F), -128.8 (d,
CF2-P, 2F). 1H NMR (dmso-d6): δ 9.93 (s, br, ArNH3þ, 3H),
7.25 (m, Ar, 4H), 7.0 (d, P-H, 1H), 2.31 (s, CH3, 3H). Anal.
Calcd for C13H11F13NO2P: C, 31.79; H, 2.25; N, 2.85. Found: C,
31.66; H, 2.26; N, 2.94.
Synthesis of [MeC6H4NH3]2[C2F5PO3]. C2F5I (13.0 g,
52.9 mmol) and C2H5MgBr (28 mL, 60 mmol in 80 mL ether)
were stirred at -78 °C in a Schlenk tube under argon. The
Grignard exchange reaction was allowed to proceed for 1 h,
after which PBr3 (14.3 g, 52.8 mmol) was added. The mixture
was then stirred at -78 °C for 6 h and then allowed to warm
to room temperature overnight. The reaction was then
quenched with water at 0 °C and washed with ether. H2O2
(35%, 12 mL) was then added, and the mixture stirred for 3 h
and then boiled for 1 h to destroy the excess H2O2. An excess
of concentrated aqueous ammonia was then added dropwise
until precipitation of NH4MgPO4 ceased. After filtration,
the solution was boiled to remove excess ammonia and
treated with Amberlyst (IR120) catiþon exchange resin in
the Hþ form to remove residual NH4 and Mg2þ ions. The
aqueous solution was then concentrated and extracted with
ether until no phosphonic acid was detected in the water layer by
31P NMR. The ether extracts were combined and pumped
down under vacuum to constant mass to give crude C2F5P-
(O)(OH)2 as a slightly yellow, viscous liquid (6.2 g, 60%
yield). A portion of the crude acid (0.50 g, 2.5 mmol) was
analyzed by quantitative conversion to the bis(p-toluidinium) salt,
by treatment with p-toluidine (0.55 g, 5.1 mmol) in methanol at
room temperature. After 2 days, colorless, crystalline plate-
lets of [MeC6H4NH3]2[C2F5PO3] (1.0 g, 97%) were obtained,
which were recrystallized from methanol. 31P NMR (dmso-
d6): δ -4.3 (t, 2JPF = 69.7 Hz). 19F NMR (dmso-d6): δ -80.9
(s, 3F, CF3), -125.8 (d, 2F, CF2-P). 1H NMR (dmso-d6):
δ 7.49 (s, br, 6H, 2ArNH3þ), 6.95 (m, 8H, Ar), 2.21 (s, 6H,
2CH3). Mp: 246 °C (dec). Anal. Calcd for C16H20F5N2O3P:
C, 46.38; H, 4.87; N, 6.76. Found: C, 46.41; H, 5.11; N, 6.79.
Synthesis of [MeC6H4NH3]2[C4F9PO3]. (a). From PBr3.
C4F9I, (4.02 g, 11.7 mmol), C2H5MgBr (11.7 mmol in 40 mL
of ether), PBr3 (3.16 g, 11.7 mmol), and p-toluidine (0.40 g,
3.7 mmol) were used in an analogous procedure to give crude
C4F9P(O)(OH)2 (2.10 g, 60%). Treatment of the crude acid
(0.50 g, 1.7 mmol) with p-toluidine (0.40 g, 3.7 mmol) in
methanol gave after 2 days crystalline [MeC6H4NH3]2-
[C4F9PO3] (0.84 g, 98%) which was recrystallized from metha-
nol. 31P NMR (dmso-d6): δ -3.8 (t, 2JPF = 71 Hz.). 19F NMR
(dmso-d6): δ -81.1 (s, 3F, CF3), -121.6 (s, 2F, CF2), -122.7
(d, 2F,CF2-P), -126.0 (s, 2F, CF2). 1H NMR (dmso-d6):
δ 8.5 (s, br, 6H, 2ArNH3þ), 7.0 (m, 8H, Ar), 2.3 (s, 6H, 2CH3).
Mp: 269 °C (dec). Anal. Calcd for C18H20F9N2O3P: C, 42.04; H,
3.92; N, 5.44; P, 6.02. Found: C, 41.87; H, 4.04; N, 5.37; P, 5.55.
(b). From PCl3. C4F9I (4.02 g, 11.7 mmol), C2H5MgBr
(11.7 mmol in 40 mL of ether), PCl3 (1.61 g, 11.7 mmol) were
used in an analogous procedure to give crude C4F9P(O)(OH)2
(1.9 g, 55%).
1
CF2), -126.0 (s, 2F, CF2), -128.1(d, 2F, CF2-P). H NMR
Synthesis of [C6H5NH3][n-C8F17PH(O)2]. The anilinium salt
was prepared in a similar procedure using C8F17I (8.10 g,
14.8 mmol), C2H5MgBr (16.0 mmol in 58 mL ether), PBr3(4.02 g,
14.8 mmol) and aniline (1.40 g, 15.0 mmol). The crude salt was
then recrystallized from chloroform/acetone, (9:1). Yield, 6.30 g,
72%. 31P NMR (dmso-d6): δ 0.81 (dt, 1JPH = 548.0 Hz, 2JPF
=
72.8 Hz). 19F NMR (dmso-d6): δ -82.6 (s, 3F, CF3), -122.7
(s, 2F, CF2), -123.1 (s, 2F, CF2),-123.3 (s, 4F, 2CF2), -124.1
1
(s, 2F, CF2), -127.6 (s, 2F, CF2), -130.2 (d, 2F, CF2-P). H
NMR (dmso-d6): δ9.8 (s, br, 3H, PhNH3þ), 7.3 (m, 5H, Ar), 6.9 (d,
1H, P-H). Mp: 155 °C (dec). Anal. Calcd for C14H9F17NO2P: C,
29.13; H, 1.57; N, 2.43. Found: C, 28.82; H, 1.51; N, 2.73.
Synthesis of [MeC6H4NH3][n-C6F13P(O)2OH]. C6F13I (3.09 g,
6.93 mmol) and C2H5MgBr (7.3 mmol in 40 mL of ether), were
reacted while stirring at -78 °C in a 100 mL Schlenk tube under
argon. The Grignard exchange reaction was allowed to proceed for
1 h after which PBr3 (1.88 g, 6.95 mmol) was added dropwise to the
cold Grignard mixture. After the addition was complete, the reac-
tion mixture was allowed to stir at -78 °C for 6 h and then warmed
to room temperature over 1 h. The mixture then cooled to 0 °C, and
25 mL water was added dropwise while stirring. The mixture was
washed with water (3 ꢀ 100 mL). The washed ether layer was then
vigorously shaken with 50 mL of 35% H2O2 and the layers allowed
to separate overnight. The ether layer was then washed free of
peroxide with water (5 ꢀ 50 mL or until the solution did not bleach
red litmus paper). The ether solution was added dropwise to a
stirring solution of p-toluidine, (1.51 g, 14.1 mmol), in 50 mL of
ether, upon which an immediate precipitate was observed. The
precipitate was filtered and washed with 10 mL of ether followed
by 10 mL of CH2Cl2, then recrystallized from H2O/methanol (1:1)
to obtain white needle like crystals of [MeC6H4NH3][C6F13P(O)2-
OH] (3.1 g, 78%). 31PNMR(dmso-d6):δ-3.58 (t, 2JPF =74.4Hz).
19F NMR (dmso-d6): δ -80.9 (s, 3F, CF3), -120.7 (s, 2F, CF2),
-122.2 (s, 2F, CF2), -122.6 (d, 2F, CF2-P), -123.2 (s, 2F, CF2),
-126.4 (s, 2F, CF2). 1H NMR (dmso-d6): δ 8.64 (s, br, 3H,
ArNH3þ), 7.17 (m, 4H, Ar), 2.28 (s, 3H, CH3). Anal. Calcd
for C13H11F13NO3P: C, 30.78; H, 2.19; N, 2.76. Found: C, 30.69; H,
2.19; N, 2.82.
Synthesis of C4F9P(O)(OH)2. Crystalline [MeC6H4NH3]2-
[C4F9PO3] (0.20 g, 0.40 mmol) was dissolved in 20 mL aqueous
Na2CO3 (0.05 M). A 0.04 mL portion of this solution was used
to obtain initial NMR spectra. The remaining solution was passed
through freshly activated Amberlyst IR120 cation exchange resin
(10 g) in the Hþ form to give a solution of pure C4F9P(O)(OH)2
which was concentrated and made up to 2 mL in a volumetric
flask. The 31P and 19F NMR spectra of this aqueous solution of
C4F9P(O)(OH)2 were in agreement with the literature.14 Peaks
for the p-toluidine group were absent in the 13C NMR spectrum.
The concentration of the phosphonic acid solution was deter-
mined by a 1 scan 31P NMR experiment and spiking with
triphenyl phosphate. Conversion to the free acid was achieved
in 98%.
Synthesis of [MeC6H4NH3][n-C8F17P(O)2OH]. C8F17I (2.99 g,
5.47 mmol), C2H5MgBr (5.85 mmol), PBr3 (1.48 g, 5.47 mmol),

1490 Inorganic Chemistry, Vol. 50, No. 4, 2011
Hosein et al.
50 mL of 35% H2O2 and p-toluidine (1.34 g, 12.5 mmol) were used
in an analogous procedure to obtain white needle like crystals of
[MeC6H4NH3][C8F17P(O)2OH] (3.0 g, 76%). 31PNMR(dmso-d6):
δ -3.6 (t, JPF = 72.3 Hz). 19F NMR (dmso-d6): δ -81.2 (s,
3F, CF3), -120.7 (s, 2F, CF2), -122.1 (s, 2F, CF2), -122.5 (s, 2F,
CF2), -122.6 (d, 2F, CF2-P), -122.8 (s, 2F, CF2), -123.3 (s, 2F,
CF2), -126.6 (s, 2F, CF2). 1H NMR (dmso-d6): δ 8.0 (s, br, 3H,
ArNH3þ), 7.1 (m, 4H, Ar), 2.27 (s, 3H, CH3), Mp: 233 °C (dec).
Anal. Calcd for C15H11F17NO3P: C, 29.67; H, 1.83; N, 2.31. Found:
C, 29.27; H, 1.73; N, 2.74.
Table 1. Selected Crystallographic Data of [p-H3CC6H4NH3]2[C2F5PO3] and [p-
H3CC6H4NH3][C8F17P(OH)O2]
[p-H3CC6H4NH3]2-
[C2F5PO3]
[p-H3CC6H4NH3]-
[C8F17P(OH)O2]
empirical formula
formula weight
temperature/K
crystal habit
crystal size/mm
crystal system
space group
a/A
C16H20F5N2O3P
414.31
C15H11F17NO3P
607.22
150.0(1)
colorless block
0.22 ꢀ 0.20 ꢀ 0.16
monoclinic
P21/c
12.922(1)
21.573(1)
6.666(1)
91.285(1)
1857.8(3)
4
150.0(1)
colorless block
0.20 ꢀ 0.20 ꢀ 0.10
monoclinic
P21/c
18.909(1)
17.485(1)
6.732(1)
98.397(1)
2201.9(4)
4
Thermal Decomposition of [C6H5NH3][C6F13PH(O)2]. [C6H5-
NH3][C6F13PH(O)2] (0.042 g, 0.088 mmol) was dissolved in
diglyme (0.4 mL), and dmso-d6 (0.1 mL) and water (0.1 mL)
were added to an NMR tube. To determine the yields, the NMR
sample was spiked with triphenyl phosphate (0.175 g, 0.536 mmol)
and 1,2-trichlorotrifluoroethane (0.0570 g, 0.302 mmol). The tube
was sealed and heated using an oil bath, decomposition of the salt
begins at 115 °C and after 4 h at this temperature 31P and 19F NMR
indicated full decomposition yielding [C6H5NH3][H2PO3] (98%) and
C6F13H (95%). 31P NMR (dmso-d6) δ 2.8, (d, JPH = 640 Hz.).
19F NMR (dmso-d6) δ -82.1 (s, 3F, CF3), -124.1 (s, 2F, CF2),
-124.4 (s, 2F, CF2),-127.3 (s, 2F, CF2),-130.0 (s, 2F, CF2),-139.4
(d, 2F, CF2-H, JFH = 52.7 Hz.). This procedure was repeated
yielding [C6H5NH3][H2PO3] (96%) and C6F13H (95%).
b/A
c/A
β/deg
V/A3
Z
Dcalc /g cm-3
1.481
0.215
1.832
0.287
μ/cm-1
λ(Mo KR)/A
F(000)
maximum θ/deg
reflections measured
unique data
Rint
reflections used
refln/param ratio
goodness of fit
R1 (all data)
wR2 (all data)
0.71069
856
30.03
18634
5437
0.0219
4324
16
1.066
0.71069
1200
30.03
18846
6437
0.0321
3877
11
0.970
Synthesis of [C6H5NH3][(C2F5)2PO2]. C2F5I (17.0 g, 69.1 mmol)
and C2H5MgCl (69.0 mmol in 30 mL of ether), were reacted while
stirring at -78 °C in a 100 mL Schlenk tube under argon. The
Grignard exchange reaction was allowed to proceed for 1 h after
which PCl3 (1.58 g, 11.5 mmol) was added dropwise to the cold
Grignard mixture. After the addition was complete, the reaction
mixture was allowed to stir at -78 °C for 20 min, then the Schlenk
tube was quickly transferred to a bath at -64 °C (CHCl3/dry ice),
where it was maintained at that temperature for 9 h and left to
gradually warm to room temperature overnight. The mixture was
immersed in an ice bath and shaken thoroughly with 35% H2O2
(10 mL). The aqueous layer was removed, and the ether layer
washed with distilled water (3 ꢀ 10 mL). The washed ether layer
was then added dropwise to a solution of aniline (0.80 g, 8.6 mmol
in 40 mL ether). The mixture was stirred for 1 h, and the ether was
pumped off leaving behind a yellow solid which was recrystallized
from chloroform/acetone (9:1) to give white needles of [C6H5NH3]-
[(C2F5)2PO2] (3.0 g, 11% based on C2F5I). 31P NMR (dmso-d6):
δ -1.3, (pentet, 2JPF = 65.4 Hz). 19F NMR (dmso-d6): δ -80.5, (s,
CF3); -125.6, (d, CF2). 1H NMR (dmso-d6): δ 9.75, (s, br, NH3þ);
7.49 (m, 2H, meta); 7.41 (m, 1H, para); 7.34 (m, 2H, ortho). 13C
NMR (dmso-d6):δ112.5, (tdq, CF2,1JCF = 287 Hz, 1JCP =126Hz,
2JCF = 35 Hz.), 119.6, (qtd, CF3, 1JCF = 287 Hz, 2JCF = 32 Hz,
2JCP = 16 Hz.), 123.5, 128.6, 130.4, 132.4. Calcd for C10H8F10NO2P:
C, 30.40; H, 2.04; N, 3.54. Found: C, 30.88; H, 2.04; N, 3.37.
Crystal Structure Determinations. [MeC6H4NH3]2[C2F5PO3]
was dissolved in hot methanol in a conical flask, and the solution
0.0384 (0.0511)
0.1078 (0.1153)
0.0469 (0.0894)
0.1251 (0.1434)
was left to crystallize by slow evaporation. Colorless crystalline
platelets were obtained after 2 days. [MeC6H4NH3][n-C8F17P-
(O)2OH] was dissolved in water/methanol (1:1), and colorless
needles were obtained by slow evaporation. Crystals were
mounted on fiberglass using paraton oil and immediately cooled
to 150 K in a cold stream of nitrogen. All data were collected on
a Nonius Kappa CCD diffractometer at 150(1) K using Mo KR
(λ=0.71073 A) X-ray source and a graphite monochromator.
The cell parameters were initially determined using more than
50 reflections. Experimental details are described in Table 1.
The crystal structures were solved in SIR 9746 and refined
in SHELXL-9747 by full-matrix least-squares using aniso-
tropic thermal displacement parameters for all non-carbon
and non-hydrogen atoms. Ortep drawings were made with
ORTEP3-v2.48
Acknowledgment. Support from a Royal Society of Chemistry
Research Fund Grant is gratefully acknowledged.
Supporting Information Available: CIF files giving X-ray
diffraction data for [MeC6H4NH3]2[C2F5PO3] and [MeC6H4NH3]-
[n-C8F17P(O)2OH]. This material is available free of charge via
the Internet at http://pubs.acs.org.
(46) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G.; Giacovazzo,
C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R. SIR97, An
integrated package of computer programs for the solution and refinement of
crystal structures using single crystal data; J. Appl. Crystallogr. 1999, 32,
115-119.
€
€
€
(47) Sheldrick, G. M. SHELXL-97; Universitat Gottingen: Gottingen,
Germany, 1997.
(48) Farrugia, L. J. Ortep-3 for Windows; J. Appl. Crystallogr. 1997, 30, 565.