Synthesis and coordination chemistry of fluorinated phosphonic acids

Article abstract of DOI:10.1016/j.jfluchem.2009.04.008

Phosphonic acids [(HO)₂P(O)C₂H₄C_nF_2n+1] (n = 4, 6) and [(HO)₂P(O)C₆H₄-4-C_nF_2n+1] (n = 0, 1, 6) have been prepared in good yields. Deprotonation a

Full text of DOI:10.1016/j.jfluchem.2009.04.008

Journal of Fluorine Chemistry 130 (2009) 615–620
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis and coordination chemistry of fluorinated phosphonic acids
*
James A. Bennett, Eric G. Hope , Kuldip Singh, Alison M. Stuart
Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK
A R T I C L E I N F O
A B S T R A C T
Article history:
Phosphonic acids [(HO)2P(O)C2H4CnF2n+1] (n = 4, 6) and [(HO)2P(O)C6H4-4-CnF2n+1] (n = 0, 1, 6) have been
prepared in good yields. Deprotonation and reaction with cis-[PtCl2(PPh3)2] affords fluorinated platinum
complexes which have been characterised by elemental analysis, mass spectrometry, IR and NMR
spectroscopies. The structures of [Pt{O2P(O)C6H4-4-F}(PPh3)2], [Pt{O2P(O)C6H4-4-CF3}(PPh3)2] and
[Pt{O2P(O)C2H4C6F13}(PPh3)2] have been determined by single crystal X-ray diffraction.
ß 2009 Elsevier B.V. All rights reserved.
Received 17 March 2009
Received in revised form 30 March 2009
Accepted 5 April 2009
Available online 3 May 2009
Keywords:
Fluorous
Phosphonic acids
Coordination chemistry
Platinum
Phosphine
X-ray structure
1. Introduction
series, the intermediate alkyldiethyl phosphonates were prepared
from the reaction of fluorinated alkyl iodides with triethylpho-
´
Since the introduction of fluorous chemistry by Horvath and
sphate, using the well established Michaelis-Arbuzov protocol
[11,12], as reported recently by Gladysz as a step in the synthesis of
some perfluoroalkylated primary phosphines [13]. For the aryl
series, the Michaelis-Arbuzov protocol proved unsuccessful for the
synthesis of the intermediate aryldiethyl phosphonates, but the
palladium(0) mediated coupling of fluorinated aryl halides with
diethylphosphonate [14] afforded the desired products in reason-
able yields. The spectroscopic data for these new compounds are
largely unremarkable, with 31P NMR chemical shifts characteristic
of the two classes of phosphorus(V) species and diastereotopic AB
1H NMR multiplets for the methylene protons of the diethyl
phosphonates. Both the fluorinated alkyl and aryl diethyl
phosphonates were hydrolysed in high yields to the corresponding
phosphonic acids with aqueous HCl.
´
Rabai in 1994 [1], there has been considerable interest in the
synthesis and applications of species incorporating long perfluor-
oalkyl substituents [2–4]. We have been particularly interested in
the electronic and steric implications of the perfluoroalkyl
substituents on the donor properties of perfluoroalkylated ligands
in coordination chemistry and the structural impact of the fluorous
ponytails on the solid state structures of the coordination
compounds [5–10]. We have also been investigating perfluor-
oalkylated
a-zirconium phosphonates as alternative fluorous
support materials that required the synthesis of fluorinated
phosphonic acid intermediates. Here, we report the synthesis of
these phosphonic acids, and some coordination chemistry,
including the single crystal X-ray structures of three platinum(II)
phosphonate coordination compounds.
The principle objective in the synthesis of these phosphonic
acids was for the generation of perfluoroalkylated
a-zirconium
phosphonates as solid supports [15]. However the amorphous
nature of these materials precluded conventional characterisation,
and we sought an alternative approach to confirm the coordination
properties and the influence of the fluorinated substituents in
these phosphonic acids. Previously, Kemmitt et al. have structu-
rally characterised the complex, [Pt{O2P(O)Ph} (PMePh2)2] as part
of a wider series of platinum(II) species [16], and this offered a
valuable range of coordination complexes for comparison pur-
poses. Reaction of the fluorinated phosphonic acids with
[PtCl2(PPh3)2] in the presence of silver oxide afforded the series
2. Results and discussion
A number of fluorinated alkyl and aryl phosphonic acids have
been prepared in moderate yields via a two-step sequence
(Scheme 1) and fully characterised by elemental analysis, mass
spectrometry and multinuclear NMR spectroscopies. For the alkyl
* Corresponding author. Tel.: +44 116 252 2108; fax: +44 116 252 3789.
E-mail address: egh1@le.ac.uk (E.G. Hope).
0022-1139/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2009.04.008

616
J.A. Bennett et al. / Journal of Fluorine Chemistry 130 (2009) 615–620
Scheme 1.
Fig. 2. Molecular structure of [Pt{O2P(O)(C6H4-4-CF3)}(PPh3)2] (14) showing the
atom labelling scheme with 50% probability ellipsoids. H-atoms are omitted for
clarity.
Fig. 1. Molecular structure of [Pt{O2P(O)(C6H4-4-F)}(PPh3)2] (13) showing the atom
labelling scheme with 50% probability ellipsoids. H-atoms are omitted for clarity.
Fig. 3. Molecular structure of [Pt{O2P(O)(C2H4C6F13)}(PPh3)2] (17) showing the
atom labelling scheme with 50% probability ellipsoids. H-atoms are omitted for
clarity.
of complexes [Pt{O2P(O)R}(PPh3)2] in good yields (Scheme 1). 31P
NMR data demonstrate that the phosphonic acids readily
coordinate to the metal centre and, although there are slight
the ‘‘O2P’’ units effectively insulate the metal centre from the
electronic influence of the fluorinated substituents.
Conclusive proof of the formation of these coordination
complexes and the electronic insulation of the ‘‘O2P’’ units arises
1
2
variations in the JPtP (PPh3) and JPtP {O2P(O)R} values (Table 1),
Table 1
˚
A direct comparison between selected NMR data, bond distances (A) and angles (8) for 13, 14, 17, [Pt{O2P(O)Ph}(PPh3)2] and [Pt{O2P(O)Ph}(PMePh2)2].
1JPtP (Hz)
2JPtP (Hz)
Pt(1)–O(2) (A)
Pt(1)–O(3) (A)
Pt(1)–P(2) (A)
Pt(1)–P(3) (A)
O(2)–Pt(1)–O(3) (8)
˚
˚
˚
˚
Complex
[Pt{O2P(O)(Ph)}(PPh3)2]a
3872
3865
3881
3867
3755
127
118
119
118
122
2.061(6)
2.064(2)
2.077(3)
2.077(5)
2.070(4)
2.072(6)
2.075(3)
2.085(3)
2.085(5)
2.102(4)
2.223(3)
2.239(2)
71.4(2)
[Pt{O2P(O)(C6H4-4-F)}(PPh3)2] (13)
[Pt{O2P(O)(C6H4-4-CF3)}(PPh3)2] (14)
[Pt{O2P(O)(C2H4C6F13)}(PPh3)2] (17)
[Pt{O2P(O)(Ph)}(PMePh2)2]b
2.2191(10)
2.2230(11)
2.217(2)
2.2385(11)
2.2373(11)
2.243(2)
71.17(10)
71.58(10)
71.8(2)
2.222(1)
2.231(1)
71.2(2)
a
J.A. Bennett and E.G. Hope, unpublished work.
Data taken from Ref. [16].
b

J.A. Bennett et al. / Journal of Fluorine Chemistry 130 (2009) 615–620
617
Table 2
Crystal data.
13
14
17
Formula
M
C49H50Cl2FO3P3Pt
1064.79
C45.5H38Cl6F3O3P3Pt
1190.46
C45H36Cl2F13O3P3Pt
1230.64
Temperature
l
150(2) K
150(2) K
150(2) K
˚
˚
˚
0.71073 A
0.71073 A
0.71073 A
Crystal system
Space group
Triclinic
Triclinic
Triclinic
P(–)1
P(–)1
P(–)1
˚
˚
˚
a = 10.742(2) A
Unit cell dimensions
a = 10.750(3) A
a = 12.762(2) A
˚
˚
˚
b = 12.715(3) A
b = 13.973(3) A
b = 12.570(2) A
˚
˚
˚
c = 19.076(4) A
c = 18.134(4) A
c = 14.618(3) A
a
b
g
= 88.632(4)8
= 80.066(4)8
= 69.989(3)8
a
b
g
= 75.523(3)8
= 89.498(3)8
= 65.859(3)8
a
b
g
= 91.262(3)8
= 96.664(3)8
= 111.477(3)8
3
3
3
˚
˚
˚
U
2292.5(9) A
2
2290.3(7) A
2
2374.9(8) A
2
Z
Dc
1.543 Mg mÀ3
3.327 mmÀ1
1068
1.788 Mg mÀ3
3.571 mmÀ1
1174
1.721 Mg mÀ3
3.258 mmÀ1
1208
m
(Mo K
a)
F(0 0 0)
Dimensions
0.23 Â 0.16 Â 0.09 mm3
0.21 Â 0.16 Â 0.06 mm3
0.21 Â 0.17 Â 0.07 mm3
Data collection range
2.02–26.008
1.76–25.008
1.75–26.008
Data collection range
À13 ꢀ h ꢀ 13
À15 ꢀ k ꢀ 15
À22 ꢀ l ꢀ 22
À15 ꢀ h ꢀ 15
À17 ꢀ k ꢀ 16
À18 ꢀ l ꢀ 18
À13 ꢀ h ꢀ 13
À15 ꢀ k ꢀ 15
À23 ꢀ l ꢀ 23
Reflections
17,788
16,683
18,537
Unique reflections
8864 [R(int) = 0.0349]
98.3%
8882 [R(int) = 0.0345]
99.1%
9192 [R(int) = 0.0388]
98.3%
Completeness of data
Absorption correction
Max/min transmission factors
Data/restraints/parameters
Goodness of fit on F2
Final R indices
Empirical
Empirical
Empirical
0.802/0.622
8864/0/451
0.987
0.862/0.651
8882/0/478
0.966
0.802/0.585
9192/400/622
1.031
R1 = 0.0294
wR2 = 0.0659
R1 = 0.0321
wR2 = 0.0657
R1 = 0.0517
wR2 = 0.1319
[I > 2s(I)]
R indices all data
R1 = 0.0351
R1 = 0.0379
R1 = 0.0645
wR2 = 0.0670
wR2 = 0.0668
wR2 = 0.1373
À3
À3
À3
À3
À3
À3
˚
˚
˚
˚
˚
˚
Largest diffraction peak and hole
1.573 eA /À1.056 eA
1.413 eA /À0.886 eA
2.259 eA /À1.256 eA
from the structural characterisation of three platinum(II) com-
plexes (Tables 1 and 2; Figs. 1–3). For (13) and (14), disordered
solvent molecules in the unit cells in these structural determina-
tions have been removed using the squeeze option in Platon [17].
These structural characterisations confirm chelation of the
phosphonic acids to the metal centre, and the Pt–O and Pt–P
bond distances and the angles in the first coordination sphere are
virtually identical for the fluoroalkyl, aryl and fluoroaryl com-
plexes. The perfluorohexyl unit in (17) radiates linearly away from
the phosphorus atom.
performed by the Elemental Analysis Service at the London
Metropolitan University. Mass spectra were recorded on a Kratos
Concept 1H mass spectrometer.
4.1.1. 3,3,3-Trifluoropropyldiethylphosphonate (1) [18]
A mixture of 1,1,1-trifluoro-3-iodo-propane (5.00 g, 0.022 mol)
and P(OEt)3 (28 cm3, 0.16 mol) was heated to 135 8C under
nitrogen for 5 h. The crude reaction mixture was separated
between Et2O (50 cm3) and H2O (50 cm3) and the aqueous layer
was washed with Et2O (2 Â 50 cm3) to ensure all product was
extracted. The solvent was removed under vacuum and the
resulting yellow liquid was Kugelro¨hr distilled (65 8C, 0.02 mmHg)
3. Conclusions
to yield the product as a yellow oil (0.460 g, 9%). 1H NMR (CDCl3):
d
A series of fluorinated and fluoroalkylated diethylphosphonates
and phosphonic acids have been readily prepared via literature
procedures. The straightforward formation of a series of platinu-
m(II) phosphonates demonstrates that the fluorine and fluor-
oalkylated substituents have no significant impact on the
coordination chemistry of these species.
1.27 (6H, t, 3JHH = 7.3 Hz, CH3), 1.88 (2H, m, CH2), 2.29 (2H, m, CH2),
4.04 (2H, ddq, 2JHH = 10.2 Hz, 3JPH = 8.2 Hz, 3JHH = 7.0 Hz, CHA), 4.07
2
3
3
(2H, ddq, JHH = 10.2 Hz, JPH = 8.5 Hz, JHH = 7.0 Hz, CHB). 31P{1H}
NMR (CDCl3):
NMR (CDCl3):
100%).
d
d
27.89 (s). 19F{1H} NMR (CDCl3):
d
À68.02 (s). 19F
3
À68.02 (3F, t, JFH = 10.4 Hz). m/z (ES+) 235 (MH+,
4. Experimental
4.1.2. 1H,1H,2H,2H-nonafluorohexyldiethylphosphonate (2)
1H,1H,2H,2H-nonafluorohexyldiethylphosphonate (2) was pre-
4.1. General experimental procedures
pared similarly as a clear oil. Yield 57%. 1H NMR (CDCl3):
d 1.28 (6H,
t, 3JHH = 7.0 Hz, CH3), 1.91 (2H, m, CH2), 2.31 (2H, m, CH2), 4.04 (2H,
ddq, 2JHH = 10.2 Hz, 3JPH = 8.2 Hz, 3JHH = 7.0 Hz, CHA), 4.10 (2H, ddq,
Proton, 13C, 19F and 31P NMR spectroscopic studies were carried
out on a Bruker DPX300 spectrometer at 300.14, 75.47, 282.41 and
121.50 MHz. All chemical shifts are quoted in ppm using the high-
frequency positive convention; 1H and 13C NMR spectra were
referenced to external SiMe4, 19F NMR spectra to external CFCl3
and 31P NMR spectra to external H3PO4. Elemental analyses were
3
3
2JHH = 10.2 Hz, JPH = 8.5 Hz, JHH = 7.0 Hz, CHB). 1H{19F} NMR
3
(CDCl3):
d
1.28 (6H, t, JHH = 7.0 Hz, CH3), 1.91 (2H, m, CH2),
2
3
2.31 (2H, m, CH2), 4.04 (2H, ddq, JHH = 10.2 Hz, JPH = 8.2 Hz,
3JHH = 7.0 Hz, CHA), 4.10 (2H, ddq, JHH = 10.2 Hz, JPH = 8.5 Hz,
2
3
3JHH = 7.0 Hz, CHB). 1H{31P} NMR (CDCl3):
d
1.28 (6H, t,

618
J.A. Bennett et al. / Journal of Fluorine Chemistry 130 (2009) 615–620
3JHH = 7.0 Hz, CH3), 1.91 (2H, m, CH2), 2.31 (2H, m, CH2), 4.04 (2H,
dq, 2JHH = 10.2 Hz, 3JHH = 7.0 Hz, CHA), 4.10 (2H, dq, 2JHH = 10.2 Hz,
4.1.6. 4-Trifluoromethylphenyldiethylphosphonate (6)
4-Trifluoromethylphenyldiethylphosphonate (6) [19] was pre-
pared similarly. Yield 69%. Anal. Calcd. for C11H14F3O3P: C, 46.8; H,
3JHH = 7.0 Hz, CHB). 13C{1H} NMR (CDCl3):
d
16.26 (d, 3JPC = 6.0 Hz,
1
2
CH3), 17.05 (d, JPC = 147.2 Hz, CH2), 25.03 (t, JFC = 22.7 Hz, CH2),
62.11 (d, JPC = 6.0 Hz, CH2). 31P{1H} NMR (CDCl3):
5.0. Found: C, 46.7; H, 5.0. 1H NMR (CDCl3):
d
1.33 (6H, t,
2
2
3
d
28.36 (s).
3JHH = 7.3 Hz, CH3), 4.03 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz,
19F{1H} NMR (CDCl3):
d
À81.04 (3F, t, JFF = 9.5 Hz, CF3), À115.53
3JHH = 7.0 Hz, CHA), 4.12 (2H, ddq, JHH = 10.2 Hz, JPH = 8.2 Hz,
4
2
3
(2F, m,
a
-CF2), À124.28 (2F, m, CF2), À126.04 (2F, m, CF2). m/z (ES+)
3JHH = 7.0 Hz, CHB), 7.65 (2H, dd, 3JHH = 8.2 Hz, 4JPH = 3.5 Hz, 3-CH),
385 (MH+, 100%).
7.88 (2H, dd, JPH = 12.9 Hz, JHH = 8.5 Hz, 2-CH).13C{1H} NMR
3
3
(CDCl3):
d
16.16 (d, 3JPC = 6.0 Hz, CH3), 62.44 (d, 2JCP = 6.0 Hz, CH2),
1
3
4.1.3. 1H,1H,2H,2H-tridecafluorooctyldiethylphosphonate (3)
1H,1H,2H,2H-tridecafluorooctyldiethylphosphonate (3) was pre-
pared similarly as a pale yellow oil. Yield 48%. Anal. Calcd. for
123.45 (q, JFC = 272.4 Hz, CF3), 125.22 (dq, JPC = 14.4 Hz,
3JFC = 3.6 Hz, 3-CH), 132.15 (d, JPC = 10.8 Hz, 2-CH), 132.76 (d,
2
1JPC = 187.9 Hz, 1-C), 133.95 (qd, JFC = 32.3 Hz, JPC = 3.6 Hz, 4-C).
2
4
C
12H14F13O3P: C, 29.8; H, 2.9. Found: C, 29.8; H, 2.7. 1H NMR
31P {1H} NMR (CDCl3):
d
16.34 (s). 19F {1H} NMR (CDCl3):
d
À63.31
3
(CDCl3):
d
1.29 (6H, t, JHH = 7.0 Hz, CH3), 1.92 (2H, m, CH2), 2.30
(s). m/z (ES+) 282 (M+, 30%).
2
3
(2H, m, CH2), 4.07 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz,
3JHH = 7.0 Hz, CHA), 4.08 (2H, ddq, JHH = 10.2 Hz, JPH = 8.5 Hz,
4.1.7. 4-Tridecafluorohexylphenyldiethylphosphonate (7)
4-Tridecafluorohexylphenyldiethylphosphonate (7) was prepared
similarly. Yield 85%. Anal. Calcd. for C16H14F13O3P: C, 36.1; H, 2.6.
2
3
3JHH = 7.0 Hz, CHB). 13C{1H} (CDCl3):
d
16.26 (d, 3JPC = 6.0 Hz, CH3),
1
18.71 (d, JPC = 143.6 Hz, CH2), 25.14 (m, CH2), 62.19 (d,
2JPC = 6.0 Hz, CH2). 31P{1H} NMR (CDCl3):
NMR (CDCl3):
d
28.38 (s). 19F{1H}
Found: C, 35.9; H, 2.5. 1H NMR (CDCl3):
CH3), 4.04 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz,
d
1.27 (6H, t, 3JHH = 7.0 Hz,
2
3
3
d
À80.80 (3F, t, 4JFF = 9.5 Hz, CF3), À115.31 (2F, m,
a
-
2
3
3
CF2), À121.90 (2F, m, CF2), À122.86 (2F, m, CF2), À123.33 (2F, m,
CHA), 4.14 (2H, ddq, JHH = 10.2 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz,
CF2), À126.12 (2F, m, CF2). m/z (ES+) 485 (MH+, 40%).
CHB), 7.62 (2H, dd, 3JHH = 8.2 Hz, 4JPH = 3.5 Hz, 3-CH), 7.89 (2H, dd,
3JHH = 8.2 Hz, JPH = 13.2 Hz, 2-CH). 1H{31P} NMR (CDCl3):
d 1.27
3
4.1.4. 1H,1H,2H,2H,3H,3H-
(6H, t, 3JHH = 7.0 Hz, CH3), 4.04 (2H, dq, 2JHH = 10.2 Hz,
2
3
heptadecafluoroundecyldiethylphosphonate (4)
1H,1H,2H,2H,3H,3H-heptadecafluoroundecyldiethylphosphonate
(4) was prepared similarly as a pale yellow oil. Yield 62%. Anal.
3JHH = 7.0 Hz, CHA), 4.14 (2H, dq, JHH = 10.2 Hz, JHH = 7.0 Hz,
CHB), 7.62 (2H, d, 3JHH = 8.2 Hz, 3-CH), 7.89 (2H, d, 3JHH = 8.2 Hz, 2-
CH). 13C{1H} NMR (CDCl3):
d
16.14 (d, 3JPC = 6.0 Hz, CH3), 62.47 (d,
Calcd. for C15H16F17O3P: C, 30.1; H, 2.7. Found: C, 30.0; H, 2.7. 1H
2JPC = 6.0 Hz, CH2) 126.86 (dt, JPC = 14.4 Hz, JFC = 6.0 Hz, 3-CH),
3
3
3
2
2
NMR (CDCl3):
d
1.26 (6H, t, JHH = 7.0 Hz, CH3), 1.75 (2H, m, CH2),
131.93 (d, JPC = 10.8 Hz, 2-CH), 132.60 (td, JFC = 23.9 Hz,
1
1.88 (2H, m, CH2), 2.15 (2H, m, CH2), 3.96–4.14 (4H, m, CH2).
4JPC = 3.6 Hz, 4-C), 133.23 (d, JPC = 167.6 Hz, 1-C). 31P{1H} NMR
13C{1H} NMR (CDCl3):
25.00 (d, JPC = 143.6 Hz, CH2), 31.04 (m, CH2), 62.00 (d,
2JPC = 7.2 Hz, CH2). 31P{1H} NMR (CDCl3):
d
14.04 (m, CH2), 16.26 (d, 3JCP = 6.0 Hz, CH3),
(CDCl3):
d
16.31 (s); 19F{1H} NMR (CDCl3):
d
a
À80.82 (3F, t,
-CF2), À121.42
1
4
4JFF = 9.5 Hz, CF3), À111.29 (2F, t, JFF = 14.2 Hz,
d
30.11 (s). 19F{1H}
(2F, m, CF2), À121.69 (2F, m, CF2), À122.79 (2F, m, CF2), À123.33
NMR (CDCl3):
d
À80.81 (3F, t, 4JFF = 10.0 Hz, CF3), À114.50 (2F, m,
(2F, m, CF2). m/z (ES+) 533 (MH+, 100%).
a
-CF2), À121.71 (2F, m, CF2), À121.92 (4F, m, CF2), À122.70 (2F, s,
CF2), À123.55 (2F, m, CF2), À126.11 (2F, m, CF2). m/z (ES+) 599
4.1.8. 1H,1H,2H,2H-nonafluorohexylphosphonic acid (8)
(MH+, 100%).
F9C4-C2H4-PO(OEt)2 (2) (3.17 g, 8.2 mmol) was refluxed
(110 8C) with vigorous stirring for 48 h in H2O (20 cm3) with
12 M HCl (20 cm3). The solvent was removed in vacuo, the white
solid was washed with chloroform and dried under vacuum to
yield the product as white powder (1.80 g, 67%). Anal. Calcd. for
C6H6F9O3P: C, 22.0; H, 1.8. Found: C, 22.1; H, 1.7. 1H NMR (C3D6O):
4.1.5. 4-Fluorophenyldiethylphosphonate (5)
A solution of Pd(PPh3)4 (2.65 g, 2.3 mmol) and F-C6H4-Br
(8.00 g, 0.046 mol) in toluene (20 cm3) was added under N2 to a
mixture of HPO(OEt)2 (6.4 cm3, 0.050 mol) and NEt3 (7.0 cm3,
0.050 mol), and the mixture was stirred at 90 8C for 3.5 h. After
cooling, Et2O (50 cm3) was added, the solution was filtered, the
solvent was removed in vacuo and the crude product was distilled
in a Kugelro¨hr to yield the product as a clear oil. Yield 69%. Anal.
d
2.05 (2H, m, CH2), 2.51 (2H, m, CH2), 10.45 (2H, s, OH). 31P{1H}
NMR (C6D6):
NMR (C3D6O):
d d
25.77 (s). 31P{1H} NMR (C3D6O): 27.56 (s). 19F{1H}
d
À81.01 (3F, t, 4JFF = 9.5 Hz, CF3), À115.90 (2F, m,
a-
CF2), À124.91 (2F, m, CF2), À126.84 (2F, m, CF2); 13C {1H} NMR
Calcd. for C10H14FO3P: C, 51.7; H, 6.0. Found: C, 51.7; H, 6.2. 1H
(C3D6O): d
18.85 (d, 1JPC = 146.0 Hz, CH2), 25.93 (m, CH2). m/z (ESÀ)
3
NMR (CDCl3):
d
1.25 (6H, t, JHH = 7.0 Hz, CH3), 4.00 (2H, ddq,
327 ([MÀH]À, 100%).
3
3
2JHH = 10.0 Hz, JPH = 7.6 Hz, JHH = 7.0 Hz, CHA), 4.06 (2H, ddq,
3
3
2JHH = 10.0 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz, CHB), 7.07 (2H, ddd,
4.1.9. 1H,1H,2H,2H-tridecafluorooctylphosphonic acid (9)
1H,1H,2H,2H-tridecafluorooctylphosphonic acid (9) was prepared
similarly. Yield 91%. Anal. Calcd. for C8H6F13O3P: C, 22.4; H, 1.4.
3JPH = 12.8 Hz, JFH = 8.8 Hz, JHH = 8.8 Hz, 2-CH), 7.75 (2H, ddd,
4
3
3JHH = 8.8 Hz, JFH = 5.5 Hz, JPH = 3.2 Hz, 3-CH). 1H{31P} NMR
3
4
3
(CDCl3):
d
1.23 (6H, t, JHH = 7.0 Hz, CH3), 4.00 (2H, dq,
Found: C, 22.6; H, 1.4. 1H NMR (C3D6O):
d
1.92 (2H, m, CH2), 2.36
(2H, m, CH2), 8.59 (2H, s, OH). 31P{1H} NMR (C3D6O):
27.81 (s).
À81.82
-CF2), À122.52 (2F, m,
2JHH = 10.0 Hz, JHH = 7.0 Hz, CHA), 4.06 (2H, dq, JHH = 10.0 Hz,
d
3
2
3JHH = 7.0 Hz, CHB), 7.07 (2H, dd, 4JFH = 8.8 Hz, 3JHH = 8.8 Hz, 2-CH),
31P{1H} NMR (C6D6):
d d
32.93 (s). 19F{1H} NMR (C3D6O):
3
3
7.75 (2H, dd, JFH = 5.5 Hz, JHH = 8.8 Hz, 3-CH). 1H{19F} NMR
(3F, t, 4JFF = 10.4 Hz, CF3), À115.66 (2F, m,
a
3
(CDCl3):
d
1.25 (6H, t, JHH = 7.0 Hz, CH3), 4.00 (2H, ddq,
CF2), À123.53 (2F, m, CF2), À123.98 (2F, m, CF2), À126.80 (2F, m,
3
3
2JHH = 10.0 Hz, JPH = 7.6 Hz, JHH = 7.0 Hz, CHA), 4.06 (2H, ddq,
CF2). 13C{1H} NMR (C3D6O): 18.91 (d, 1JPC = 149.6 Hz, CH2), 25.95
d
3
3
2JHH = 10.0 Hz, JPH = 7.9 Hz, JHH = 7.0 Hz, CHB), 7.07 (2H, dd,
(m, CH2). m/z (ESÀ) 427 ([MÀH]À, 100%).
3JPH = 12.8 Hz, JHH = 8.8 Hz, 2-CH), 7.75 (2H, dd, JHH = 8.8 Hz,
3
3
4JPH = 3.5 Hz, 3-CH). 13C{1H} NMR (CDCl3):
d
16.23 (d, 3JPC = 6.0 Hz,
4.1.10. 4-Fluorophenylphosphonic acid (10)
2
3
CH3), 62.17 (d, JPC = 6.0 Hz, CH2), 115.79 (dd, JPC = 15.6 Hz,
4-Fluorophenylphosphonic acid (10) [19] was prepared similarly.
Yield 89%. Anal. Calcd. for C6H6FO3P: C, 40.9; H, 3.4. Found: C, 40.8;
2JFC = 21.5 Hz, 3-CH), 124.4 (d, JPC = 193.2 Hz, 1-C), 134.33 (dd,
1
2JPC = 10.8 Hz, JFC = 8.4 Hz, 2-CH), 165.53 (d, JFC = 252.8 Hz, 4-C).
H, 3.3. 1H NMR (C3D6O): 7.25 (2H, ddd, 3JFH = 8.5 Hz, 3JHH = 8.5 Hz,
d
3
1
31P{1H} NMR (CDCl3):
(s). m/z (ES+) 232 (M+, 80%).
d
18.36 (s). 19F{1H} NMR (CDCl3):
d
À106.04
4JPH = 2.9 Hz, 3-CH), 7.85 (2H, ddd, JPH = 13.1 Hz, JHH = 8.7 Hz,
3
3
4JFH = 5.8 Hz, 2-CH), 10.17 (2H, s, OH). 13C{1H} NMR (C3D6O):
d

J.A. Bennett et al. / Journal of Fluorine Chemistry 130 (2009) 615–620
619
2
3
116.20 (dd, JFC = 21.4 Hz, JPC = 15.2 Hz, 3-CH), 134.45 (dd,
4.1.15. Platinum bis(triphenylphosphine)(4-
tridecafluorohexylphenylphosphonate) [Pt{O2P(O)C6H4-4-
C6F13}(PPh3)2] (15)
3
2JPC = 12.0 Hz, JFC = 8.2 Hz, 2-CH). 31P{1H} NMR (C3D6O):
d
17.08
(s). 31P{1H} NMR (D2O):
d
15.14 (s). 19F{1H} NMR (C3D6O):
d
À109.22 (s). m/z (ES+) 177 (MH+, 30%); m/z (ESÀ) 175 ([MÀH]À,
Platinum
phosphonate) [Pt{O2P(O)C6H4-4-C6F13}(PPh3)2] (15) was prepared
similarly as white powder. Yield 85%. Anal. Calcd. for
bis(triphenylphosphine)(4-tridecafluorohexylphenyl-
100%).
a
4.1.11. 4-Trifluoromethylphenylphosphonic acid (11)
C
48H34F13O3P3Pt: C, 48.3; H, 2.8. Found: C, 48.2; H, 2.7. 1H NMR
4-Trifluoromethylphenylphosphonic acid (11) [19] was prepared
similarly. Yield 67%. Anal. Calcd. for C7H6F3O3P: C, 37.2; H, 2.7.
(CD2Cl2):
NMR (CD2Cl2):
4JFF = 14.2 Hz,
d
7.09–7.36 (30H, m, Ph), 7.54–7.85 (4H, m, Ar). 19F{1H}
4
d
a
À81.06 (3F, t, JFF = 10.4 Hz, CF3), À110.77 (2F, t,
Found: C, 37.0; H, 2.6. 1H NMR (C3D6O):
d
7.13 (2H, s, OH), 7.75–
7.91 (m, 2H), 8.01 (m, 2H); 31P {1H} NMR (C3D6O): 15.37 (s); 31
14.06 (s). 19F{1H} NMR (C3D6O):
À63.73 (s,
123.92 (q, JFC = 272.3 Hz, CF3),
-CF2), À121.50 (2F, m, CF2), À122.01 (2F, m, CF2),
d
P
À122.91 (2F, m, CF2), À126.33 (2F, m, CF2). 31P{1H} NMR (CD2Cl2):
d
{1H} NMR (C6D6):
d
d
7.3 (s, JPtP = 3886 Hz, PPh3), 37.3 (t, JPtP = 117 Hz, PO3). 13C{1H}
1
2
CF3). 13C{1H} NMR (C3D6O):
d
NMR (CD2Cl2): d 126.40 (m, CH), 127.78 (m, C), 128.81 (m, CH),
1
3
2
2
126.05 (d, JPC = 10.8 Hz, 3-CH), 132.46 (d, JPC = 9.6 Hz, 2-CH),
132.80 (q, 2JFC = 32.3 Hz, 4-C), 137.23 (d, 1JPC = 184.1 Hz, 1-C). m/z
(ESÀ) 225 ([MÀH]À, 100%).
131.26 (d, JPC = 9.4 Hz, 2-CH), 131.89 (m, CH), 132.25 (m, C),
1
134.67 (m, CH), 144.90 (d, JCP = 160.1 Hz, 1-C). m/z (FAB) 1194
(MH+, 100%).
4.1.12. 4-Tridecafluorohexylphenylphosphonic acid (12)
4.1.16. Platinum bis(triphenylphosphine)(1H,1H,2H,2H-
4-Tridecafluorohexylphenylphosphonic acid (12) was prepared
similarly. Yield 97%. Anal. Calcd. for C12H6F13O3P: C, 30.3; H, 1.3.
nonafluorohexylphosphonate) [Pt{O2P(O)C2H4C4F9}(PPh3)2] (16)
Platinum bis(triphenylphosphine)(1H,1H,2H,2H-nonafluorohexyl-
phosphonate) [Pt{O2P(O)C2H4C4F9}(PPh3)2] (16) was prepared simi-
larly as a white powder. Yield 75%. Anal. Calcd. for C42H34F9O3P3Pt:
Found: C, 30.2; H, 1.2. 1H NMR (C3D6O):
d 7.72 (2H, dd,
4
3
3JHH = 8.5 Hz, JPH = 2.9 Hz, 3-CH), 7.94 (2H, dd, JPH = 13.2,
3JHH = 8.5 Hz, 2-CH), 8.01 (2H, s, OH). 31P{1H} NMR (C3D6O):
d
d
-
C, 48.2; H, 3.3. Found: C, 48.2; H, 3.4. 1H NMR (CD2Cl2):
d 1.67 (2H,
15.20 (s). 31P{1H} NMR (C6D6):
d
19.59 (s). 19F{1H} NMR (C3D6O):
m, CH2), 2.26 (2H, m, CH2), 7.13–7.37 (30H, m, Ph). 19F{1H} NMR
À81.70 (3F, t, 4JFF = 10.4 Hz, CF3), À111.41 (2F, t, 4JFF = 14.2 Hz,
a
(CDCl3):
d
À81.29 (3F, t, 4JFF = 9.5 Hz, CF3), À115.52 (2F, m,
a-CF2),
CF2), À122.00 (2F, m, CF2), À122.20 (2F, m, CF2), À123.47 (2F, m,
À124.42 (2F, m, CF2), À126.11 (2F, m, CF2). 31P{1H} NMR (CD2Cl2):
d
CF2), À126.83 (2F, m, CF2). 13C{1H} NMR (C3D6O):
d
127.71 (dt,
7.0 (s, 1JPtP = 3856 Hz, PPh3), 45.12 (s, 2JPtP = 110 Hz, PO3). 13C{1H}
3JPC = 14.6 Hz, 3JFC = 6.1 Hz, 3-CH), 132 .33 (d, 2JPC = 10.8 Hz, 2-CH).
m/z (ESÀ) 475 (MHÀ, 100%).
NMR (CD2Cl2):
d
22.14 (d, JPC = 199.3 Hz, CH2), 27.29 (d,
1
2JPC = 22.1 Hz, CH2), 127.50 (m, C), 128.41 (m, CH), 131.45 (m,
CH), 134.20 (m, CH). m/z (FAB) 1046 (MH+, 100%).
4.1.13. Platinum bis(triphenylphosphine)(4-
fluorophenylphosphonate) [Pt{O2P(O)C6H4-4-F}(PPh3)2] (13)
F-C6H4-PO(OH)2 (0.074 g, 41.8 mmol) and silver(I) oxide
(0.580 g, 251 mmol) were added in succession to a stirred
solution of [PtCl2(PPh3)2] (0.330 g, 41.8 mmol) in dichloro-
methane (40 cm3) and the mixture was refluxed for 4 h. The
cooled reaction mixture was filtered and the filtrate was
evaporated to dryness under reduced pressure to yield the
product as a white powder, which was recrystallised from
dichloromethane-light petroleum and dried in vacuo (0.343 g,
92%). Anal. Calcd. for C42H34FO3P3Pt: C, 56.4; H, 3.8. Found: C,
4.1.17. Platinum bis(triphenylphosphine)(1H,1H,2H,2H-
tridecafluorooctylphosphonate) [Pt{O2P(O)C2H4C6F13}(PPh3)2] (17)
Platinum bis(triphenylphosphine)(1H,1H,2H,2H-tridecafluorooc-
tylphosphonate) [Pt{O2P(O)C2H4C6F13}(PPh3)2] (17) was prepared
similarly as a white powder. Yield 73%. 1H NMR (CDCl3):
d 1.76 (2H,
m, CH2), 2.30 (2H, m, CH2), 7.07–7.45 (30H, m, Ph). 19F{1H} NMR
(CDCl3):
d
À80.71 (3F, t, 4JFF = 9.5 Hz, CF3), À115.11 (2F, m,
a-CF2),
À121.77 (2F, m, CF2), À122.78 (2F, m, CF2), À123.40 (2F, m, CF2),
À126.04 (2F, m, CF2). 31P{1H} NMR (CDCl3):
d
6.8 (s, 1JPtP = 3867 Hz,
21.59
PPh3), 47.3 (t, 2JPtP = 118 Hz, PO3). 13C {1H} NMR (CD2Cl2):
d
1
2
55.3; H, 3.6. 1H NMR (CD2Cl2):
d
6.93–7.02 (2H, m, 2-CH), 7.10–
(d, JPC = 121.5 Hz, CH2), 27.21 (d, JPC = 23.6 Hz, CH2), 127.85 (m,
C), 128.78 (m, CH), 131.82 (m, CH), 134.58 (m, CH). m/z (FAB) 1145
[M+] 70%.
7.37 (30H, m, Ph), 7.66–7.76 (2H, m, 3-CH). 19F{1H} NMR
(CD2Cl2):
d
À112.9 (s). 31P{1H} NMR (CD2Cl2):
d 7.3 (d,
1JPtP = 3865, JPP = 7 Hz, PPh3), 37.3 (t, JPtP = 118 Hz, JPP = 7 Hz,
3
2
3
PO3). 13C{1H} NMR (CD2Cl2):
d
114.71 (dd, JFC = 20.6 Hz,
4.2. Crystal structures of [Pt{O2P(O)C6H4-4-F}(PPh3)2],
2
3JPC = 14.4 Hz, 3-CH), 127.96 (m, C), 128.76 (m, CH), 131.84 (m,
[Pt{O2P(O)C6H4-4-CF3}(PPh3)2] and [Pt{O2P(O)C2H4C6F13}(PPh3)2]
2
3
CH), 133.28 (dd, JPC = 10.5 Hz, JFC = 7.8 Hz, 2-CH), 134.68 (m,
CH), 136.58 (dd, 1JPC = 165.2 Hz, 4JFC = 3.6 Hz, 1-C). m/z (FAB) 894
(MH+, 100%).
Crystals of 13, 14 and 17 were grown by slow evaporation from
DCM/petroleum ether solutions. Full details of the data collection
and refinement are given in Table 2. Data were collected on a
Bruker APEX 2000 CCD diffractometer using graphite-monochro-
4.1.14. Platinum bis(triphenylphosphine)(4-
trifluoromethylphenylphosphonate) [Pt{O2P(O)C6H4-4-CF3}(PPh3)2]
(14)
mated Mo Ka radiation.
Platinum bis(triphenylphosphine)(4-trifluoromethylphenylpho-
sphonate) [Pt{O2P(O)C6H4-4-CF3}(PPh3)2] (14) was prepared simi-
larly as a white powder. Yield 91%. Anal. Calcd. for C43H34F3O3P3Pt:
4.3. Structure solution and refinement
Structure solution by Patterson methods and structure refine-
ment on F2 employed SHELXTL Version 6.10 (SHELXTL, an
integrated system for solving, refining and displaying crystal
structures) [20]. The C–H hydrogen atoms were included in
C, 54.7; H, 3.6. Found: C, 54.6; H, 3.8. 1H NMR (CD2Cl2):
d
7.09–7.36
À62.8
(30H, m, Ph), 7.54–7.85 (4H, m, Ar). 19F{1H} NMR (CD2Cl2):
d
1
(s). 31P{1H} NMR (CD2Cl2):
d
7.2 (s, JPtP = 3881 Hz, PPh3), 32.7 (s,
2JPtP = 119 Hz, PO3). 13C{1H} NMR (CD2Cl2):
d
123.45 (q,
calculated positions (C–H = 0.96 A) with isotropic displacement
˚
1JFC = 272.4 Hz, CF3), 124.32 (dq, JPC = 13.2 Hz, JFC = 3.6 Hz, 3-
parameters set to 1.2 Ueq of the bonded atom. All non-hydrogen
atoms were refined with anisotropic displacement parameters.
The data were corrected for Lorentz and polarisation effects and
empirical absorption corrections applied. For (13) and (14) the
SQUEEZE option in PLATON [17] was used to remove disordered
3
3
2
CH), 127.44 (m, C), 128.41 (m, CH), 130.54 (qd, JFC = 31.6 Hz,
4JPC = 3.0 Hz, 4-C), 130.76 (d, JPC = 9.4 Hz, 2-CH), 131.48 (m, CH),
134.68 (m, CH), 144.90 (d, JPC = 159.3 Hz, 1-C). m/z (FAB) 944
2
1
(MH+, 100%).

620
J.A. Bennett et al. / Journal of Fluorine Chemistry 130 (2009) 615–620
[4] J.A. Gladysz, D.P. Curran, I.T. Horva´th (Eds.), Handbook of Fluorous Chemistry,
Wiley-VCH, Weinheim, 2004.
[5] J. Fawcett, E.G. Hope, R.D.W. Kemmitt, D.R. Paige, D.R. Russell, A.M. Stuart, J. Chem.
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(1999) 2913.
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491.
[8] B. Croxtall, J. Fawcett, E.G. Hope, A.M. Stuart, J. Fluorine Chem. 119 (2003) 65.
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[10] D.J. Adams, J.A. Bennett, D. Duncan, E.G. Hope, J. Hopewell, A.M. Stuart, A.J. West,
Polyhedron 26 (2007) 1505.
solvent molecules. For (17) the H atoms of the disordered CH2Cl2
were not included in the model but were included in all formulae.
Crystallographic data (excluding structure factors) for the struc-
tures in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.’s
CCDC 680044-680046. Copies of the data can be obtained, free of
charge, on application to CCDC, 12 Union Road, Cambridge CB2
1EZ, UK (fax: +44 1223 336033 or e-mail: deposit@ccdc.cam.a-
c.uk).
[11] A.E. Arbuzov, J. Russ. Phys. Chem. Soc. 38 (1906) 687.
[12] A. Michaelis, R. Kaehne, Chem. Berl. 31 (1898) 1048.
[13] C. Emnet, J.A. Gladysz, Synthesis 6 (2005) 1012.
[14] T. Hirao, T. Masunaga, N. Yamada, Y. Oshiro, T. Agawa, Bull. Chem. Soc. Jpn. 55
(1982) 909.
[15] J.A. Bennett, E.G. Hope, manuscript in preparation.
[16] R.D.W. Kemmitt, S. Mason, J. Fawcett, D.R. Russell, J. Chem. Soc. Dalton Trans.
(1992) 851.
Acknowledgements
We would like to thank the Royal Society (AMS), the EPSRC
(JAB) and Merck (JAB) for financial support.
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