Synthesis and coordination chemistry of fluorinated xanthate ligands

Article abstract of DOI:10.1016/j.jfluchem.2005.03.022

Alkali metal, copper, nickel and rhodium complexes of alkylated [S ₂COC₈H₁₇] and fluoroalkylated xanthate ligands [S₂COC_mH_2mC_nF_2n+1] (m = 2, n = 4, 6; m = 3, n = 1, 8) have been prepared in high yields and characterised by elemental analysis, mass spectrometry, IR and NMR spectroscopies. The structures of [Cu(S₂COC₈H ₁₇)(PPh₃)₂], [Cu(S₂COC ₃H₆CF₃)(PPh₃)₂], [Ni(S₂COC₃H₆CF₃)₂], [Cp*RhCl(S₂COC₈H₁₇)] and [Cp*RhCl(S₂COC₃H₆CF₃)] have been determined by single crystal X-ray diffraction.

Full text of DOI:10.1016/j.jfluchem.2005.03.022

Journal of Fluorine Chemistry 126 (2005) 1117–1124
www.elsevier.com/locate/fluor
Synthesis and coordination chemistry of fluorinated xanthate ligands
*
John Fawcett, Eric G. Hope , Alison M. Stuart, Dan R.W. Wood
Department of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, UK
Received 11 March 2005; accepted 17 March 2005
Available online 24 May 2005
Dedicated to Professor Herbert W. Roesky on the occasion of his 70th birthday.
Abstract
Alkali metal, copper, nickel and rhodium complexes of alkylated [S2COC8H17] and fluoroalkylated xanthate ligands [S2COCmH2mCnF2n+1
]
(m = 2, n = 4, 6; m = 3, n = 1, 8) have been prepared in high yields and characterised by elemental analysis, mass spectrometry, IR and NMR
spectroscopies. The structures of [Cu(S2COC8H17)(PPh3)2], [Cu(S2COC3H6CF3)(PPh3)2], [Ni(S2COC3H6CF3)2], [Cp*RhCl(S2COC8H17)]
and [Cp*RhCl(S2COC3H6CF3)] have been determined by single crystal X-ray diffraction.
# 2005 Elsevier B.V. All rights reserved.
Keywords: Fluorous; Xanthates; Coordination chemistry; X-ray structure
1. Introduction
trifluoroethylxanthate ligand [11], including its coordination
chemistry with nickel(II) [12] and, most recently, radical
allylation chemistry [13].
We have been evaluating the electronic and steric
implications of fluorine substituents on the donor properties
of fluorinated ligands in coordination chemistry and the
structural impact of these units on the solid state structures
of the coordination compounds [1–9]. In contrast to the
extensive coordination chemistry of fluorinated neutral P-,
N- and O-donor ligands [10], there have been relatively few
reports on charged fluorinated ligands. In this area, we have
shown that zinc and nickel perfluoroalkylated b-diketonate
complexes can be used in catalysis and recycled using
fluorous solid phase extraction techniques [8] and, most
recently, that perfluoroalkylated dithiophosphates can be
readily prepared and coordinated to a range of late transition
metals [9]. Here, we extend this work to a second class of
perfluoroalkylated sulfur donor ligands with the synthesis,
and subsequent coordination chemistry, of some fluoroalky-
lated xanthate ligands, including the single crystal X-ray
structures of copper(I), nickel(II) and rhodium(III) xanthate
coordination compounds. Previous work on fluorinated
xanthate ligands has been largely restricted to the 2,2,2-
2. Results and discussion
The classical routes to alkali metal xanthates, either in the
absence of solvent or using an excess of the alcohol as the
solvent, are not readily adaptable to the use of long chain
perfluoroalcohols, and we used diethyl ether as a convenient,
unreactive solvent for the synthesis of a series of long chain
alkali metal xanthates (1–5); these offer convenient starting
materials for the subsequent coordination chemistry. In the
absence of structural and spectroscopic data for related long
chain perprotioxanthate ligands and their coordination
complexes, as part of this work potassium O-octylxanthate
(1), with a C8H17 sidechain, has been prepared and
characterised.
We have previously used copper(I) phosphine [6,9] and
pentamethylcyclopentadienyl rhodium(III) [1,3,4] units for
investigations of the coordination properties of various
classes of perfluoroalkylated ligands. The reaction of the
sodium or potassium xanthates (1–5) with either
[Cu(NO3)(PPh3)2] or [Cp*RhCl2]2 in methanol or dichloro-
* 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 # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2005.03.022

Table 1
Crystal data
6
9
11
13
15
Formula
C45H47CuOP2S2
793.43
C41H36CuF3OP2S2
791.30
C19H32ClORhS2
478.93
C15H21ClF3ORhS2
476.80
C10H12F6NiO2S4
465.15
M
Temperature
l
160(2) K
˚
0.71073 A
160(2) K
˚
0.71073 A
160(2) K
˚
0.71073 A
160(2) K
˚
0.71073 A
183(2) K
˚
0.71073 A
Crystal system
Space group
Unit cell dimensions
Triclinic
Monoclinic
P2(1)/c
˚
a = 10.8112(10) A,
Triclinic
Monoclinic
P2(1)/c
˚
a = 16.7126(12) A,
Triclinic
P(À)1
P(À)1
P(À)1
˚
a = 10.2969(5) A,
˚
a = 7.4794(3) A,
˚
a = 6.123(1) A,
˚
b = 13.3013(6) A,
˚
b = 19.9411(19) A,
˚
b = 13.4425(5) A,
˚
b = 7.4689(5) A,
˚
b = 7.5168(12) A,
˚
c = 15.1633(7) A,
˚
c = 17.4493(17) A,
˚
c = 22.7306(9) A,
˚
c = 15.7575(11) A,
˚
c = 18.639(3) A,
a = 79.978(1)8,
b = 77.611(1)8,
g = 85.034(1)8
b = 105.546(2)8
a = 73.420(1)8,
b = 86.859(1)8,
g = 82.052(1)8
b = 111.935(1)8
a = 96.067(3)8,
b = 95.838(3)8,
g = 98.736(3)8
3
3
˚
3
3
˚
3
˚
˚
˚
U
1994.87(16) A
3624.2(6) A
2169.03(15) A
1824.5(2) A
837.1(2) A
Z
2
4
4
4
2
Dc
1.321 MgmÀ3
0.766 mmÀ1
832
1.450 MgmÀ3
0.855 mmÀ1
1632
1.467 MgmÀ3
1.107 mmÀ1
992
1.736 MgmÀ3
1.338 mmÀ1
960
1.845 MgmÀ3
1.719 mmÀ1
468
m (Mo Ka)
F(0 0 0)
Dimensions
0.38 mm  0.32 mm
 0.27 mm
1.39–27.00o
À13 ꢀ h ꢀ 13,
À16 ꢀ k ꢀ 16,
À19 ꢀ l ꢀ 19
16581
0.28 mm  0.21 mm
 0.19 mm
1.58–26.5o
À13 ꢀ h ꢀ 13,
À25 ꢀ k ꢀ 25,
À21 ꢀ l ꢀ 21
29150
0.38 mm  0.19 mm
 0.15 mm
0.93–26.00o
À9 ꢀ h ꢀ 9,
À16 ꢀ k ꢀ 16,
À27 ꢀ l ꢀ 27
16918
0.36 mm  0.23 mm
 0.17 mm
1.31–25.038
À19 ꢀ h ꢀ 19,
À8 ꢀ k ꢀ 8,
À18 ꢀ l ꢀ 18
12121
0.24 mm  0.18 mm
 0.06 mm
2.21–26.008
À7 ꢀ h ꢀ 7,
À9 ꢀ k ꢀ 9,
À22 ꢀ l ꢀ 22
6632
Data collection range
Data collection range
Reflections
Unique reflections
8497 [R(int) = 0.0172]
97.6%
7516 [R(int) = 0.0592]
100.0%
8398 [R(int) = 0.0177]
98.6%
3218 [R(int) = 0.0186]
99.8%
3258 [R(int) = 0.0358]
99.1%
Completeness of data
Absorption correction
Maximum/minimum
transmission factors
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2s(I)]
R indices all data
Empirical
Empirical
Empirical
Empirical
Empirical
0.898/0.805
0.88/0.84
0.862/0.736
0.85/0.69
0.92/0.74
8497/0/461
7516/0/451
8398/0/445
3218/0/276
3258/0/208
1.117
1.090
1.046
1.073
0.807
R1 = 0.0370, wR2 = 0.1059
R1 = 0.0421, wR2 = 0.1083
R1 = 0.0314, wR2 = 0.0926
R1 = 0.0353, wR2 = 0.0941
R1 = 0.0257, wR2 = 0.0665
R1 = 0.0291, wR2 = 0.0686
R1 = 0.0203, wR2 = 0.0528
R1 = 0.0214, wR2 = 0.0535
R1 = 0.0435, wR2 = 0.0748
R1 = 0.0702, wR2 = 0.0809
À3
À3
À3
À3
À3
˚
˚
˚
˚
˚
Largest diff. peak and hole
1.138/À0.566 eA
0.633/À0.412 eA
0.754/À0.512 eA
0.370/À0.449 eA
0.654/À0.351 eA

J. Fawcett et al. / Journal of Fluorine Chemistry 126 (2005) 1117–1124
1119
Scheme 1. Synthesis of coordination compounds of the xanthate ligands.
Table 2
˚
A direct comparison between selected bond distances (A) and angles (8) for 6, 9 and [Cu{S2P(OC2H4C4F9)2}(PPh3)2], [Cu{S2P(OC8H17)2}(PPh3)2] and
[Cu{C7F15C(O)CHC(O)C7F15}(PPh3)2]
6
9
[Cu(L-L)(PPh3)2]a
[Cu(L-L)(PPh3)2]b
[Cu(L-L)(PPh3)2]c
Cu–P(1)
2.2284(5)
2.2582(5)
2.4221(5)
2.3987(5)
1.6899(19)
1.6872(19)
2.2142(5)
2.2458(5)
2.4067(5)
2.4083(5)
1.6735(17)
1.6782(17)
2.261(1)
2.2629(8)
2.2390(9)
Cu–P(2)
2.275(1)
2.2781(8)
2.2480(9)
Cu–S(1)
2.530(1)
2.5148(8)
–
Cu–S(2)
2.404(1)
2.4084(8)
–
S(1)–C(1)
S(2)–C(1)
P(2)–Cu–P(1)
S(1)–Cu–S(2)
O(1)–Cu–O(2)
–
–
–
–
–
–
128.81(2)
75.110(17)
–
118.847(18)
74.789(15)
–
127.44(5)
125.85(3)
128.34(3)
83.67(4)
83.63(3)
–
–
–
–
–
86.73(8)
S(1)–C(1)–S(1)
a
120.95(11)
L-L = S2P(OC2H4C4F9)2À; Ref. [9].
121.49(10)
–
L-L = S2P(OC8H17 2
L-L = C7F15C(O)CHC(O)C7F15À; Ref. [6].
)
À; Ref. [9].
b
c
Table 4
methane, respectively, generated the desired [Cu(L-
L)(PPh3)2] (6–10) or [Cp*RhCl(L-L)] (11–14) species in
good yields (Scheme 1) and these have been characterised by
elemental analysis and spectroscopic studies. Although
copper(I) phosphine xanthate complexes of this type have
not been described previously, methyl- and ethyl-xanthate
˚
A direct comparison between selected bond distances (A) and angles (8) for
15, [Ni(S2COCH2CF3)2] and [Ni(S2COC6H4-4-tBu)2]
15
[Ni(S2COCH2CF3)2]a [Ni(S2COC6H4-4-tBu)2]b
Ni(1)–S(1) 2.2197(12) 2.211(4)
Ni(1)–S(2) 2.2135(12) 2.203(5)
Ni(1)–S(3) 2.2164(12) 2.223(5)
Ni(1)–S(4) 2.2029(12) 2.218(4)
2.219(4)
2.213(6)
2.222(7)
2.205(5)
1.670(27)
1.699(19)
1.676(210
1.687(30)
79.1(2)
S(1)–C(5)
S(2)–C(5)
S(3)–C(6)
S(4)–C(6)
1.689(4)
1.688(4)
1.684(4)
1.696(4)
1.69(1)
1.70(1)
1.71(2)
1.68(2)
79.2(2)
Table 3
˚
Selected bond distances (A) and angles (8) for 11 and 13
11(Mol. 1)
11 (Mol. 2)
13
Rh–Cp(centroid)
Rh(1)–S(1)
1.783
1.779
1.785
S(2)–Ni(1) 79.21(4)
–S(1)
2.3812(6)
2.3910(5)
2.4050(6)
1.688(2)
1.689(2)
72.855(19)
89.79(2)
93.74(2)
114.12(12)
2.3871(6)
2.3828(5)
2.4078(6)
1.688(2)
1.690(2)
72.983(19)
91.06(2)
92.83(2)
114.21(11)
2.3942(5)
2.4005(5)
2.4053(5)
1.691(2)
1.689(2)
Rh(1)–S(2)
S(4)–Ni(1) 79.02(4)
–S(3)
79.0(2)
113(1)
114(1)
79.4(2)
113.7(10)
114.4(11)
Rh(1)–Cl(1)
S(1)–C(1)
S(1)–C(1) 113.6(2)
–S(2)
S(2)–C(1)
S(1)–Rh(1)–S(2)
S(1)–Rh(1)–Cl(1)
S(2)–Rh(1)–Cl(1)
S(1)–C(1)–S(1)
72.711(17)
91.786(19)
91.691(19)
114.47(11)
S(3)–C(6) 112.5(2)
–S(4)
a
Ref. [12].
b
Ref. [19].

1120
J. Fawcett et al. / Journal of Fluorine Chemistry 126 (2005) 1117–1124
rhodium(III) derivatives, [Cp*RhCl(S2COR)] (R = Me, Et)
have been briefly described [14]. We were also interested in
the synthesis of homoleptic metal xanthate complexes and
reaction of NaS2COC3H6CF3 with NiCl2 in ethanol readily
afforded an example of a square planar [Ni(L-L)2] (15)
derivative; the related fully protonated bis(n-butylxanthate)-
nickel(II) complex has been reported previously [15]. The
data for all of these complexes are unremarkable, entirely
consistent with the formulations and literature data
[6,9,12,14,15] and indicate that the fluorinated substituents
have a negligible impact upon the coordination chemistry of
these derivatised xanthate ligands.
In the absence of definitive spectroscopic data for metal
xanthate complexes, single crystal structural characterisa-
tion has been used extensively in this area. Here, we have
obtained single crystals suitable for X-ray structural analysis
for [Cu(L-L)(PPh3)2] and [Cp*RhCl(L-L)] (L-L = S2CO-
C8H17, S2COC3H6CF3), and [Ni(S2COC3H6CF3)2]; crystal
data are listed in Table 1. Selected bond length and angles for
these complexes, together with data for related complexes,
are listed in Tables 2–4 and molecular structures are
reproduced in Figs. 1–5. The complexes adopt the anti-
cipated pseudo tetrahedral, piano stool and square planar
Fig. 2. Molecular structure of [Cu(S2COC3H6CF3)(PPh3)2] (9) showing the
atom labelling scheme with 50% probability ellipsoids. H-atoms are omitted
for clarity.
Fig. 1. Molecular structure of [Cu(S2COC8H17)(PPh3)2] (6) showing the
atom labelling scheme with 50% probability ellipsoids. H-atoms are omitted
for clarity.
Fig. 3. Molecular structure of one of the unique molecules of
[Cp*RhCl(S2COC8H17)] (11) showing the atom labelling scheme with
50% probability ellipsoids. H-atoms are omitted for clarity.

J. Fawcett et al. / Journal of Fluorine Chemistry 126 (2005) 1117–1124
1121
the analogous homoleptic complexes, [Ni(S2COR)2]
(R = C2H5 [18], CH2CF3 [12], C6H4-4-tBu [19]). The angles
subtended by the xanthate ligands are relatively acute and
increase in the series Rh < Cu < Ni in line with the steric
bulk around the metal centres. Interestingly, the S–Cu–S
bond angles are substantially smaller for these copper
xanthate complexes than those for the closely related copper
dithiophosphate complexes [9], presumably as a con-
sequence of changing carbon for phosphorus in the
metallocyclic ring. The most striking difference between
the structural data for these complexes lies in the S–C–S
angle within the xanthate ligands. For the copper complexes,
the angles are close to that expected within a trigonal plane,
1208, whilst those for the rhodium and nickel complexes are
substantially smaller (112–1148). Strikingly, the data for the
pairs of complexes indicates that neither the complex
geometry nor the structural parameters are affected by the
introduction of the fluorine atoms.
3. Conclusions
Fig. 4. Molecular structure of [Cp*RhCl(S2COC3H6CF3)] (13) showing the
atom labelling scheme with 50% probability ellipsoids. The dotted bonds
show the disorder of the chain. H-atoms are omitted for clarity.
The reaction of long chain alcohols with CS2 in the
presence of base affords alkali metal xanthates in good
yields. Coordination of these ligands to a number of late
transition metal centres is straightforward and spectroscopic
and structural data indicate that the fluorinated substituents
do not impact upon the coordination properties or the
coordination modes adopted by this ligand class.
geometries. Two independent molecules exist in the unit cell
of [Cp*RhCl(S2COC8H17)] (11), one with a regular octyl
sidechain and the other with a kinked or bent sidechain,
although the metal coordination environments for both
molecules are, essentially, identical. The 4,4,4-trifluorobutyl
sidechain in [Cp*RhCl(S2COC3H6CF3)] (13) is disordered
over two sites within the crystal, but this has no impact upon
the metal coordination sphere. In [Ni(S2COC3H6CF3)2]
(15), the two sidechains are different; one is linear whilst the
second adopts a boat configuration. In all five structures, the
xanthate ligands chelate symmetrically to the metal centres.
For the copper and rhodium complexes, the M–S bond
4. Experimental
4.1. General experimental procedures
Proton, 19F and 31P NMR spectroscopic studies were
carried out on a Bruker ARX250 spectrometer at 250.13,
235.34 and 101.26 MHz or a Bruker DPX300 spectrometer
at 300.14, 282.41 and 121.50 MHz. All chemical shifts are
quoted in ppm using the high-frequency positive convention;
1H NMR spectra were referenced to external SiMe4, 19F
NMR spectra to external CFCl3 and 31P NMR spectra to
˚
lengths (ca. 2.4 A) are comparable to those seen for a variety
of heteroleptic metal xanthate complexes with ethyl,
isopropyl or isopentyl substituents [16,17]. In contrast,
the Ni–S bond lengths in 15 are significantly shorter (ca.
˚
2.2 A), and these are virtually identical to those reported for
Fig. 5. Molecular structure of [Ni(S2COC3H6CF3)2] (15) showing the atom labelling scheme with 50% probability ellipsoids. H-atoms are omitted for clarity.

1122
J. Fawcett et al. / Journal of Fluorine Chemistry 126 (2005) 1117–1124
external H3PO4. The infrared spectra were recorded on a
Digilab FTS40 Fourier transform spectrometer at 4 cmÀ1
resolution for compounds as Nujol mulls held between KBr
discs. Elemental analyses were performed either by
Butterworth Laboratories Ltd. or the Elemental Analysis
Service at the University of North London. Mass spectra
were recorded on a Kratos Concept 1H mass spectrometer.
Dichloromethane, dried by refluxing over CaH2, and
diethyl ether, dried by refluxing over sodium metal, were
distilled under nitrogen, stored in closed ampoules over
molecular sieves and freezed/pumped/thawed three times to
remove all dissolved gases before use. The [Cu(PPh3)2(NO3)]
was prepared by the literature route [20], whilst
1H,1H,2H,2H-tridecafluoro-n-octanol, 1H,1H,2H,2H-nona-
fluoro-n-hexanol (Fluorochem) and [Cp*RhCl2]2 (Aldrich)
were used as supplied.
1241 cmÀ1 (vs). Anal. Calcd for C9H4F13KOS2: C, 22.6; H,
0.8; S, 13.4. Found: C, 22.4; H, 0.9; S, 13.4.
4.1.4. Sodium{O-(4,4,4-trifluoro-n-butyl)xanthate} (4)
Sodium{O-(4,4,4-trifluoro-n-butyl)xanthate} (4) was pre-
1
pared similarly. Yield 69%. H NMR (D2O): d 4.60 (2H, t,
3JH–H = 6.7 Hz, a-CH2), 2.52(2H, m,g-CH2), 2.15(2H, m,b-
CH2). 19F{1H} NMR (D2O): d À66.41 (3F, s, CF3). MS (ES)
m/z: 203 [C5H6F3OS2À]. IR (Nujol): 1105 cmÀ1 (s),
1152 cmÀ1 (s). Anal. Calcd for C5H6F3NaOS2: C, 26.6; H,
2.7; S, 28.4. Found: C, 26.1; H, 2.7; S, 27.0.
4.1.5. Potassium{O-(1H,1H,2H,2H,3H,3H-
heptadecafluoro-n-undecyl)xanthate} (5)
Potassium{O-(1H,1H,2H,2H,3H,3H-heptadecafluoro-n-
undecyl)xanthate} (5) was prepared similarly. Yield 73%.
3
1H NMR (CD3OD): d 4.49 (2H, t, JH–H = 6.9 Hz, a-CH2),
4.1.1. Potassium(O-octyl xanthate) (1)
2.32 (2H, m, g-CH2), 1.98 (2H, m, b-CH2). 19F{1H} NMR
4
Carbon disulfide (2.92 g, 38.4 mmol), potassium hydro-
xide (2.15 g, 38.4 mmol) and octanol (50 cm3) were stirred
rapidly at room temperature for 2 h to give the product as a
yellow precipitate (7.53 g, 80%). 1H NMR (CD3COCD3): d
(CD3OD): d À81.01 (3F, t, JF–F = 9.0 Hz, CF3), À114.12
(2F, m, a-CF2), À121.49 (2F, m, CF2), À122.41 (6F, m,
CF2), À123.10 (2F, m, CF2), À125.86 (2F, m, CF2). MS (ES)
m/z: 553 [C12H6F17OS2À]. IR (Nujol): 1093 cmÀ1 (s),
1149 cmÀ1 (s), 1203 cmÀ1 (s), 1221 cmÀ1 (s).
3
4.42 (2H, t, JH–H = 7.0 Hz, a-CH2), 1.92 (2H, m, b-CH2),
1.51 (10H, m, CH2), 1.13 (3H, t, 3JH–H = 7.0 Hz, CH3). MS
(ES) m/z: 177 [C9H17OS2À]. IR (Nujol): 1040 cmÀ1 (w),
1057 cmÀ1 (s), 1115 cmÀ1 (s), 1138 cmÀ1 (s), 1161 cmÀ1
(sh).
4.1.6. Copper bis(triphenylphosphine)(O-octylxanthate)
[Cu{S2COC8H17}(PPh3)2] (6)
Potassium O-octylxanthate (1) (0.400 g, 1.64 mmol) and
[(PPh3)2Cu(NO3)] (1.061 g, 1.64 mmol) in methanol were
rapidly stirred for 30 mins at room temperature. After
concentration of the solution in vacuo, the product was
isolated as a yellow solid by filtration and washed with cold
methanol (1.022 g, 79%). 1H NMR (CDCl3): d 7.43 (30H, m,
4.1.2. Potassium{O-(1H,1H,2H,2H-nonafluoro-n-
hexyl)xanthate} (2)
Potassium hydride (0.455 g, 13.6 mmol) was added
carefully to
a
stirred solution of 1H,1H,2H,2H-
3
nonafluorohexanol (3.000 g, 13.6 mmol) and carbon disulfide
(0.865 g, 13.6 mmol) in diethyl ether (30 cm3), and the
solution stirred at room temperature for 2 h with the evolution
of hydrogen to give the product as a pale yellow precipitate
Ph), 4.51 (2H, t, JH–H = 7.0 Hz, a-CH2), 1.92 (2H, m, b-
3
CH2), 1.40 (10H, m, CH2), 1.03 (3H, t, JH–H = 7.0 Hz,
CH3). 31P{1H} NMR (CDCl3): d 0.1 (s). IR (Nujol):
1056 cmÀ1 (w), 1093 cmÀ1 (w), 1141 cmÀ1 (s), 1162 cmÀ1
(s), 1178 cmÀ1 (s).
1
3
(2.01 g, 39%). H NMR (CD3COCD3): d 4.51 (2H, t, JH–
H = 7.1 Hz, a-CH2), 2.43 (2H, m, b-CH2). 19F{1H} NMR
(CD3COCD3): d À82.39(3F, t, 4JF–F = 9.3 Hz, CF3), À114.08
4.1.7. Copper bis(triphenylphosphine)(O-
1H,1H,2H,2H-nonafluoro-n-hexylxanthate)
4
(2F, t, JF–F = 11.0 Hz, a-CF2), À124.84 (2F, m, g-CF2),
À126.39 (2F, m, b-CF2). MS (ES) m/z: 339 [C7H4F9OS2À].
IR (Nujol): 1058 cmÀ1 (w), 1081 cmÀ1 (w), 1110 cmÀ1 (s),
1138 cmÀ1 (vs), 1219 cmÀ1 (s), 1240 cmÀ1 (s). Anal. Calcd
for C7H4F9KOS2: C, 22.2; H, 1.1; S, 17.0. Found: C, 22.0; H,
1.3; S, 16.7.
[Cu{S2COC2H4C4F9}(PPh3)2] (7) was prepared simi-
larly as a yellow solid. Yield 57%. 1H NMR (CDCl3): d 7.10
(30H, m, Ph), 4.47 (2H, t, 3JH–H = 7.1 Hz, a-CH2), 2.41 (2H,
m, b-CH2). 19F{1H} NMR (CDCl3): d À81.37 (3F, t,
4
4JF–F = 9.3 Hz, CF3), À114.01 (2F, t, JF–F = 11.0 Hz, a-
CF2), À124.83 (2F, m, g-CF2), À126.35 (2F, m, b-CF2).
31P{1H} NMR (CDCl3): d 1.0 (s). IR (Nujol): 1095 cmÀ1
(w), 1135 cmÀ1 (s), 1160 cmÀ1 (w), 1226 cmÀ1 (s). Anal.
Calcd for C43H34CuF9OP2S2: C, 55.7; H, 3.7; P, 6.7; S, 6.9.
Found: C, 55.7; H, 3.8; P, 6.3; S, 6.9.
4.1.3. Potassium{O-(1H,1H,2H,2H-tridecafluoro-n-
octyl)xanthate} (3)
Potassium{O-(1H,1H,2H,2H-tridecafluoro-n-octyl)-
1
xanthate} (3) was prepared similarly. Yield 50%. H NMR
3
(CD3COCD3): d 4.83 (2H, t, JH–H = 6.9 Hz, a-CH2), 2.84
(2H, m, b-CH2). 19F{1H} NMR (CD3COCD3): d À80.81 (3F,
t,4JF–F = 9.0 Hz, CF3), À112.78(2F, m, a-CF2), À121.50(2F,
m, CF2), À122.49 (2F, m, CF2), À123.19 (2F, m, CF2),
À125.83 (2F, m, CF2). MS (ES) m/z: 439 [C9H4F13OS2À]. IR
(Nujol): 1113 cmÀ1 (s), 1142 cmÀ1 (vs), 1205 cmÀ1 (vs),
4.1.8. Copper bis(triphenylphosphine)(O-
1H,1H,2H,2H-tridecafluoro-n-octylxanthate)
[Cu{S2COC2H4C6F13}(PPh3)2] (8) was prepared simi-
larly as a yellow solid. Yield 86%. 1H NMR (CDCl3): d 7.41
(30H, m, Ph), 4.84 (2H, t, 3JH–H = 7.0 Hz, a-CH2), 2.70 (2H,

J. Fawcett et al. / Journal of Fluorine Chemistry 126 (2005) 1117–1124
1123
3
m, b-CH2). 19F{1H} NMR (CDCl3): d À81.03 (3F, t,
4.70 (2H, t, JH–H = 6.9 Hz, a-CH2), 2.58 (2H, m, b-CH2),
1.72 (15H, s, Cp*). 19F{1H} NMR (CDCl3): d À81.29 (3F, t,
4JF–F = 10.1 Hz, CF3), À113.70 (2F, m, a-CF2), À122.30
(2F, m, CF2), À123.27 (2F, m, CF2), À123.85 (2F, m, CF2),
À126.54 (2F, m, CF2). MS (FAB) m/z: 677 [M À Cl+]. IR
(Nujol): 1025 cmÀ1 (w), 1145 cmÀ1 (s), 1237 cmÀ1 (vs).
Anal. Calcd for C19H19ClF13O2RhS2: C, 32.0; H, 2.7; S, 9.0.
Found: C, 32.2; H, 2.6; S, 9.0.
4
4JF–F = 9.3 Hz, CF3), À113.74 (2F, t, JF–F = 11.8 Hz, a-
CF2), À122.33 (2F, m, CF2), À123.18 (2F, m, CF2), À123.80
(2F, m, CF2), À126.49 (2F, m, CF2). 31P{1H} NMR
(CDCl3): d 1.0 (s). IR (Nujol): 1094 cmÀ1 (w), 1144 cmÀ1
(s), 1167 cmÀ1 (w), 1185 (s), 1211 cmÀ1 (s), 1232 cmÀ1 (s).
Anal. Calcd for C45H34CuF13OP2S2: C, 52.6; H, 3.3; P, 6.0;
S, 6.2. Found: C, 52.6; H, 3.4; P, 6.0; S, 6.3.
4.1.9. Copper bis(triphenylphosphine)
(O-4,4,4-trifluoro-n-butylxanthate)
4.1.13. Pentamethylcyclopentadienylrhodium(O-4,4,4-
trifluoro-n-butylxanthate)chloride
[Cu{S2COC3H6CF3}(PPh3)2] (9) was prepared similarly
[Cp*RhCl(S2COC3H6CF3)] (13) was prepared similarly
1
1
as a dark red solid. Yield 91%. H NMR (CDCl3): d 4.45
as a yellow solid. Yield 98%. H NMR (CDCl3): d 7.24
(30H, m, Ph), 4.30 (2H, t, 3JH–H = 6.6 Hz, a-CH2), 2.21 (2H,
m, g-CH2), 1.95 (2H, m, b-CH2). 19F{1H} NMR (CDCl3): d
À66.61 (3F, s, CF3). 31P{1H} NMR (CDCl3): d 0.8 (s). IR
(Nujol): 1027 cmÀ1 (w), 1058 cmÀ1 (w), 1094 cmÀ1 (w),
1169 cmÀ1 (s). Anal. Calcd for C41H36CuF3OP2S2: C, 62.2;
H, 4.6; P, 7.8; S, 8.2. Found: C, 61.8; H, 4.3; P, 7.2; S, 7.3.
(2H, t, JH–H = 6.8 Hz, a-CH2), 2.24 (2H, m, g-CH2), 1.98
3
(2H, m, b-CH2), 1.67 (15H, s, Cp*). 19F{1H} NMR (CDCl3):
d À66.72 (3F, s, CF3). MS (FAB) m/z: 411 [M À Cl+]. IR
(Nujol): 1024 cmÀ1 (w), 1133 cmÀ1 (s), 1251 cmÀ1 (s).
Anal. Calcd for C15H21ClF3O2RhS2: C, 37.8; H, 4.4; S, 13.4.
Found: C, 38.1; H, 4.3; S, 12.0.
4.1.10. Copper bis(triphenylphosphine)
(O-1H,1H,2H,2H,3H,3H-heptadecafluoro-n-
undecylxanthate)
4.1.14. Pentamethylcyclopentadienylrhodium
(O-1H,1H,2H,2H-heptadecafluoro-n-
undecylxanthate)chloride
[Cu{S2COC3H6C8F17}(PPh3)2] (10) was prepared simi-
larly as a yellow solid. Yield 66%. 1H NMR (CDCl3): d 7.23
(30H, m, Ph), 4.34 (2H, t, 3JH–H = 7.0 Hz, a-CH2), 2.16 (2H,
m, g-CH2), 1.99 (2H, m, b-CH2). 19F{1H} NMR (CDCl3): d
[Cp*RhCl(S2COC3H6C8F17)] (14) was prepared simi-
1
larly as a dark red solid. Yield 77%. H NMR (CDCl3): d
3
4.24 (2H, t, JH–H = 6.9 Hz, a-CH2), 2.09 (2H, m, g-CH2),
1.82 (2H, m, b-CH2), 1.57 (15H, s, Cp*). 19F{1H} NMR
(CDCl3): d À81.18 (3F, t, 4JF–F = 9.9 Hz, CF3), À114.71 (2F,
m, a-CF2), À122.29 (2F, m, CF2), À123.37 (6F, m, CF2),
À123.78 (2F, m, CF2), À126.51 (2F, m, CF2). MS (FAB) m/
z: 791 [M À Cl+]. IR (Nujol): 1025 cmÀ1 (w), 1145 cmÀ1
(s), 1238 cmÀ1 (vs).
4
À81.21 (3F, t, JF–F = 9.3 Hz, CF3), À114.70 (2F, t,
4JF–F = 11.8 Hz, a-CF2), À122.14 (2F, m, CF2), À123.08
(6F, m, CF2), À123.66 (2F, m, CF2), À126.54 (2F, m, CF2).
31P{1H} NMR (CDCl3): d 0.3 (s). IR (Nujol): 1061 cmÀ1 (w),
1095 cmÀ1 (w), 1148 cmÀ1 (s), 1203 cmÀ1 (s), 1241 cmÀ1
(s). Anal. Calcd for C48H36CuF17OP2S2: C, 50.5; H, 3.2; P,
5.4; S, 5.6. Found: C, 50.3; H, 3.4; P, 5.6; S, 5.5.
4.1.15. Nickel bis(O-4,4,4-trifluoro-n-butylxanthate)
[Ni(S2COC3H6CF3)2] (15)
4.1.11. Pentamethylcyclopentadienylrhodium
Nickel(II) chloride (0.256 g, 1.08 mmol) in water
(20 cm3) was added slowly to a slurry of sodium O-4,4,4-
trifluoro-n-butylxanthate (0.243 g, 1.07 mmol) in ethanol
(30 cm3) and the mixture stirred for 3 h to give the product as
(O-octylxanthate)chloride [Cp*RhCl(S2COC8H17)] (11)
Pentamethylcyclopentadienyl rhodium dichloride dimer
(0.1 g, 0.16 mmol) was added to a slurry of potassium
O-octylxanthate (1) (70.0 mg, 0.32 mmol) in dichloro-
methane (30 cm3) and the mixture stirred at room
temperature for 2 h. The solution was filtered, washed with
water (3 Â 20 cm3) and dried over MgSO4. Removal of the
solvent in vacuo afforded the product as a dark red solid
1
a yellow precipitate (0.322 g, 65%). H NMR (CDCl3): d
3
4.48 (2H, t, JH–H = 6.7 Hz, a-CH2), 2.21 (2H, m, g-CH2),
1.99 (2H, m, b-CH2). 19F{1H} NMR (CDCl3): d À66.67 (3F,
s, CF3). MS (FAB) m/z: 464 [M+]. IR (Nujol): 1025 cmÀ1
(w), 1086 cmÀ1 (s), 1133 cmÀ1 (s). Anal. Calcd for
C10H12F6NiO2S4: C, 25.8; H, 2.6; S, 27.6. Found: C,
26.1; H, 2.5; S, 26.9.
(0.091 g, 59%). 1H NMR (CDCl3): d 4.37 (2H, t, JH–
3
H = 7.0 Hz, a-CH2), 1.71 (15H, s, Cp*), 1.52 (2H, m, b-
CH2), 1.24(10H, m, CH2), 0.79 (3H, t, 3JH–H = 7.0 Hz, CH3).
MS (FAB) m/z: 443 [M À Cl+]. IR (Nujol): 1024 cmÀ1 (w),
1218 cmÀ1 (w), 1260 cmÀ1 (s). Anal. Calcd for
C19H32ClO2RhS2: C, 47.7; H, 6.7; S, 13.4. Found: C,
47.8; H, 6.4; S, 13.1.
4.1.16. Crystal structures of [Cu(S2COC8H17)(PPh3)2],
[Cu(S2COC3H6CF3)(PPh3)2], [Cp*RhCl(S2COC8H17)],
[Cp*RhCl(S2COC3H6CF3)] and [Ni(S2COC3H6CF3)2]
Crystals of 6 and 9 were grown by slow evaporation from
methanol solutions, and crystals of 11, 13 and 15 by slow
evaporation from acetone solutions. Full details of data
collection and refinement are given in Table 1. Data were
collected on a Bruker APEX 2000 CCD diffractometer using
graphite monochromated Mo Ka radiation.
4.1.12. Pentamethylcyclopentadienylrhodium
(O-1H,1H,2H,2H-tridecafluoro-n-octylxanthate)chloride
[Cp*RhCl(S2COC2H4C6F13)] (12) was prepared simi-
1
larly as a dark red solid. Yield 70%. H NMR (CDCl3): d

1124
J. Fawcett et al. / Journal of Fluorine Chemistry 126 (2005) 1117–1124
[2] P. Bhattacharyya, J. Fawcett, J.H. Holloway, E.G. Hope, G.C. Saun-
ders, J. Chem. Soc., Dalton Trans. (1997) 199.
[3] J. Fawcett, E.G. Hope, R.D.W. Kemmitt, D.R. Paige, D.R. Russell,
A.M. Stuart, J. Chem. Soc., Dalton Trans. (1998) 3751.
[4] E.G. Hope, R.D.W. Kemmitt, D.R. Paige, A.M. Stuart, D.R.W. Wood,
Polyhedron 18 (1999) 2913.
4.1.17. Structure solution and refinement
Structure solution by Patterson methods and structure
refinement on F2 employed SHELXTL Version 6.10
(SHELXTL, an integrated system for solving, refining
and displaying crystal structures) [21]. The C–H hydrogen
˚
atoms were included in calculated positions (C–H = 0.96 A)
[5] B. Croxtall, J. Fawcett, E.G. Hope, A.M. Stuart, J. Chem. Soc., Dalton
Trans. (2002) 491.
with isotropic displacement parameters set to 1.2Ueq of the
bonded atom. All non-hydrogen atoms were refined with
anisotropic displacement parameters. The data were
corrected for Lorentz and polarisation effects. Crystal-
lographic data (excluding structure factors) for the structures
in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication
nos. CCDC 266969–266973. 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.ac.uk).
[6] B. Croxtall, J. Fawcett, E.G. Hope, A.M. Stuart, J. Fluorine Chem. 119
(2003) 65.
[7] E.G. Hope, A.M. Stuart, A.J. West, Green Chem. 6 (2004) 345.
[8] B. Croxtall, E.G. Hope, A.M. Stuart, Chem. Commun. (2003)
2430.
[9] J. Fawcett, E.G. Hope, A.M. Stuart, D.R.W. Wood, J. Fluorine Chem.
126 (4) (2005) 507.
´
[10] J.A. Gladysz, D.P. Curran, I.T. Horvath (Eds.), Handbook of Fluorous
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ˇ
We would like to thank the Royal Society (EGH, AMS),
the EPSRC (DRWW) and Castrol International Ltd.
(DRWW) for financial support.
´ ´ˇ
´ˇ
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