Synthesis and coordination chemistry of perfluoroalkyl-derivatised β-diketonates

Article abstract of DOI:10.1016/S0022-1139(02)00251-8

A series of fluorinated β-diketones, R_fC(O)CH₂C(O)R_f′ (R_f = C₆F₁₃, R_f′ = CF₃; R_f = R_f′ = C₆F₁₃, C₇F₁₅), have been prepared in reasonable yields by a two-step synthesis. On reaction with appropriate metal substrates deprotonation and concurrent coordination of the perfluoroalkyl-derivatised β-diketonate ligands affords a range of fluorous metal complexes which have been characterised by elemental analysis, mas spectrometry, IR and NMR spectroscopies. The structures of [Cu(L-L)₂(H₂O)₂] {L-L = CF₃C(O)CHC(O)C₆F₁₃, C₆F₁₃C(O)CHC(O)C₆F₁₃}.

Full text of DOI:10.1016/S0022-1139(02)00251-8

Journal of Fluorine Chemistry 119 (2003) 65±73
Synthesis and coordination chemistry of
per¯uoroalkyl-derivatised b-diketonates
*
Ben Croxtall, John Fawcett, Eric G.Hope , Alison M.Stuart
Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK
Received 22 July 2002; received in revised form 9 September 2002; accepted 9 September 2002
Dedicated to Professor Tatlow on the occasion of his 80th birthday.
Abstract
0
0
0
A series of ¯uorinated b-diketones, RfC(O)CH2C(O)Rf (Rf ˆ C6F13, Rf ˆ CF3; Rf ˆ Rf ˆ C6F13, C7F15), have been prepared in
reasonable yields by a two-step synthesis.On reaction with appropriate metal substrates, deprotonation and concurrent coordination of the
per¯uoroalkyl-derivatised b-diketonate ligands affords a range of ¯uorous metal complexes which have been characterised by elemental
analysis, mass spectrometry, IR and NMR spectroscopies.The structures of [Cu(L±L) (H2O)2] {L±L ˆ CF3C(O)CHC(O)C6F13,
2
C6F13C(O)CHC(O)C6F13} and [Cu(PPh3)2{C7F15C(O)CHC(O)C7F15}] have been determined by single-crystal X-ray diffraction.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Fluorous; b-Diketonate ligands; Coordination chemistry; X-ray structure
1. Introduction
chemistry or applications in catalysis were reported at that
time.We have a long-standing interest in the coordination
properties of ¯uorine containing ligands and have investi-
gated a broad range of substituted phosphorus(III) ligands
[11±17].Here, we describe the synthesis of two new ¯uori-
nated diketones, alongside C7F15C(O)CH2C(O)C7F15 [10],
and the coordination chemistry of these pre-ligands with a
range of late transition metals, including the ®rst crystal
structural characterisations of coordination compounds
incorporating b-diketonate ligands with long per¯uoroalkyl
substituents.
The coordination chemistry of ¯uorinated b-diketonate
ligands, particularly the 1,1,1,5,5,5-hexa¯uoropentanedio-
nato or hexa¯uoroacac (hfacac) ligand, has been extensively
investigated for many years [1], with interest stemming from
the potential application of the volatile homoleptic transition
metal hexa¯uoroacac complexes in metal organic chemical
vapour deposition.More recently, Carlini and coworkers [2]
have investigated the activity and selectivity of [Ni{C3F7-
C(O)CHC(O)C3F7}2Á2DMF] in the dimerisation of propy-
lene to 2,3-dimethylbutenes and Knochel and coworkers
[3,4] have brie¯y introduced the application of b-diketonate
ligands with long per¯uoroalkyl (C7F15) groups for metal
catalysed oxidations under ¯uorous biphase conditions.
The ¯uorous biphase approach is an attractive solution to
the catalyst/product separation issues in homogeneous
catalysis, as it exploits the physical properties of many
per¯uorinated and conventional organic solvent mixtures,
and reports on a broad spectrum of catalytic processes
have appeared [5±9].Interestingly, the ®rst b-diketones
containing long per¯uoroalkyl substituents were synthesised
by Tatlow and coworkers in 1971 [10], but no coordination
2. Results and discussion
The reaction of the commercially available per¯uoroalky-
lated carboxylic acids with three equivalents of MeMgBr
readily affords the related methyl ketones [18].Further
reaction with the same or a different per¯uoroalkylated
ester in the presence of base gives the desired b-diketones
in moderate yields (Scheme 1).These diketones have been
probed by a range of spectroscopic techniques, including
highly characteristic 19F NMR spectra which reveal either
one (2,3) or two (1) CF3 signals and four or ®ve multiplets
assigned as CF2 resonances. 1H NMR spectroscopic studies
indicates that the ketone-enol tautomerisation is highly
solvent dependent; the enol proton appearing as a broad,
* Corresponding author.Tel:. ‡44-116-252-2108;
fax: ‡44-116-252-3789.
E-mail address: egh1@le.ac.uk (E.G. Hope).
0022-1139/02/$ ± see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 2 ) 0 0 2 5 1 - 8

66
B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
Scheme 1.
concentration dependent, singlet around 9 ppm in CDCl3
[19].
that reveal second order spectra arising from strongly
coupled diastereotopic a-CF2 ¯uorine atoms which indicate
a cis-octahedral structure for the hydrated [Zn(L±
L)2(H2O)2].
Treatment of the b-diketones with representative metal(II)
salts readily affords the per¯uoroalkylated analogues of well
established metal acac complexes (Scheme 2) which have
been characterised by elemental analysis and a range of
spectroscopic techniques.However, the homoleptic com-
plexes containing Tatlow and Knochel's per¯uoroheptyl b-
diketonate were dif®cult to characterise since they are
insoluble in most common organic solvents and are only
slightly soluble in ethereal solvents.The square planar
palladium(II) complex with the unsymmetrical ligand (5a)
adopts a 1:1 mixture of cis-/trans-isomers in solution with
two singlets for the a-CF3 groups, two triplets for the
terminal CF3 groups and two overlapping triplets for the
a-CF2 groups in the 19F NMR spectrum.The per¯uoroalkyl
groups in the zinc(II) complexes (7a±c) are equivalent and
unremarkable, indicating that these adopt regular tetrahedral
geometries and are unsolvated.This is in direct contrast to
the 19F NMR spectroscopic studies on the closely related
tetradeca¯uorononane-4,5-dionato-zinc(II) complexes [20]
Single crystal structure determinations of metal com-
plexes with ¯uorous ponytails are still relatively rare in
the literature.Here, we have crystallographically charac-
terised bis aqua adducts of two of the homoleptic b-dike-
tonate copper compounds (4a) and (4b) containing two or
four C6F13 units, respectively (Figs.1 and 2 , Table 1) and the
heteroleptic copper compound (8b) which contains two
C7F15 units (Fig.3 , Table 2).The hydrated complexes of
(4a) and (4b) were generated during the slow crystallisations
from ether solutions of the complexes over a layer of
chloroform.Full re®nement of all three structures was
complicated by considerable disorder in the per¯uoroalkyl
units and this is discussed later.
As expected for d9 copper(II) metals, the coordination
around the metal centres (which lie on crystallographic
centres of symmetry) show tetragonally distorted octahedral
arrangements of the six oxygen donors with the Cu±O bond
Scheme 2.

B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
67
Fig.1. Molecular structure of [Cu{CF 3C(O)CHC(O)C6F13}2(H2O)2] showing the atom labelling scheme with 50% probability ellipsoids.H atoms are shown
as spheres of arbitrary radii.Primed atoms indicate disorder of the CF 3 group over three sites.The molecule is located on an inversion centre, ( Ã) atoms are
generated by symmetry (1 À x, Ày, Àz).
distances for the more weakly bound axial water ligands
approximately 20% longer than those for the b-diketonate
ligands.The metal coordination environments for the two
complexes are both effectively identical to that observed in
the closely related [Cu(tdf)2(H2O)2] {tdf ˆ tetradeca¯uor-
ononane-4,6-dionato; C3F7C(O)CHC(O)C3F7} [20].For the
symmetrical copper complex with the pentadecanedianato
ligands, both C6F13 ponytails exhibit considerable disorder
beyond the a-CF2 groups.Although we have observed the
same sort of disorder in other metal complexes of per¯uor-
oalkylated ligands, the quality of the data has allowed us, for
the ®rst time, to be able to model static disorder indicating
the random distribution of a series of arrangements of the
ponytails throughout the crystal lattice rather than dynamic
Table 1
Ê
A direct comparison between selected bond distances (A) and angles (8) for [Cu{CF3C(O)CHC(O)C6F13}2(H2O)2] and
[Cu{C6F13C(O)CHC(O)C6F13}2(H2O)2]
[Cu{CF3C(O)CHC(O)C6F13}2(H2O)2]
[Cu{C6F13C(O)CHC(O)C6F13}2(H2O)2]
Cu±O(1)
Cu±O(2)
Cu±O(3)
O(1)±C(2)
O(2)±C(4)
C(2)±C(3)
C(3)±C(4)
C(1)±C(2)
C(4)±C(5)
av.C±F
1.942(3)
1.939(3)
2.334(3)
1.234(6)
1.262(5)
1.387(7)
1.369(7)
1.506(7)
1.528(6)
13. 33
Cu±O(1)
Cu±O(2)
Cu±O(3)
1.9567(16)
1.9485(16)
2.369(2)
1.257(3)
1.256(3)
1.382(3)
1.389(3)
1.544(3)
1.539(3)
O(1)±C(2)
O(2)±C(9)
C(1)±C(2)
C(1)±C(9)
C(2)±C(3)
C(9)±C(10)
av.C±F
13. 75
O(1)±Cu±O(2)
O(1)±Cu±O(3)
O(2)±Cu±O(3)
O(1)±Cu±O(20)
C(2)±O(1)±Cu
C(4)±O(2)±Cu
92.02(13)
90.93(13)
91.67(14)
87.98(13)
124.9(3)
O(1)±Cu±O(2)
O(1)±Cu±O(3)
O(2)±Cu±O(3)
O(1)±Cu±O(20)
C(2)±O(1)±Cu
C(9)±O(2)±Cu
92.38(7)
88.14(7)
90.08(7)
87.62(7)
124.54(16)
124.68(16)
124.0(3)
O(3)±H(3B)ÁÁÁO(2)
O(3)±H(3C)ÁÁÁO(1)
2.241 (1 À x, 1 À y, Àz)
2.392 (x, 1 ‡ y, z)
O(3)±H(3A)ÁÁÁO(2)
2.478 (x, 1 ‡ y, z)

68
B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
Fig.2.Molecular structure of [Cu{C 6F13C(O)CHC(O)C6F13}2(H2O)2] showing the atom labelling scheme with 50% probability ellipsoids.H atoms are
shown as spheres of arbitrary radii.Primed atoms and dashed bonds indicate disorder.The molecule is located on an inversion centre, ( Ã) atoms are generated
by symmetry (1 À x, Ày, 1 À z).
thermal liberation of the CF2 units.We have modelled the
disorder of the ¯uorine atoms on C(4), C(5), C(6), C(7),
C(13), C(14) and C(15) over two sites with 50:50 occupancy,
and also the terminal CF3 unit at C(8) {together with F(11),
F(12) and F(13)} also over two sites with 50:50 occupancy.
For the unsymmetrical copper complex with the decanedio-
nato ligands, the C6F13 ponytails exhibit no disorder and
adopt the regular linear arrangement with torsion angles
along the carbon backbone between 160 and 1708, but the a-
CF3 group is disordered across three sites (with 50:30:20
occupancies) in a well-recognised ``propeller'' pattern.For
both the structures, extended views indicate that the per-
¯uoroalkyl substituents line up in ``¯uorous domains'' but,
in view of the degree of disorder, the accurate identi®cation
of genuine short non-bonded FÁÁÁF contacts in these structure
determinations is not possible.The crystal packing diagram
of [Cu{CF3C(O)CHC(O)C6F13}2(H2O)2] also reveals that
its molecules are stacked down the b-axis with adjacent
molecules linked by four intermolecular hydrogen bonds
from the water hydrogen atoms to the oxygen atoms of the
per¯uoroalkylated b-diketonates.A similar effect is also
observed in the crystal packing diagram of [Cu{C6F13-
C(O)CHC(O)C6F13}2(H2O)2] but only two hydrogen bonds
link the adjacent molecules.
Table 2
Ê
Selected bond distances (A) and angles (8) for [Cu(PPh3)2{C7F15C(O)CH-
C(O)C7F15}] (8b)
[Cu(PPh3)2{C7F15C(O)CHC(O)C7F15}]
Cu±O(1)
Cu±O(2)
Cu±P(1)
2.119(2)
2.118(2)
2.2390(9)
2.2480(9)
1.247(4)
1.240(4)
1.399(5)
1.391(5)
1.546(4)
1.547(5)
13. 46
O(1)±Cu±O(2)
O(1)±Cu±P(1)
O(2)±Cu±P(1)
O(1)±Cu±P(2)
O(2)±Cu±P(2)
P(1)±Cu±P(2)
C(1)±O(1)±Cu
C(3)±O(2)±Cu
86.73(8)
109.68(6)
106.70(7)
116.01(6)
98.86(7)
128.34(3)
125.3(2)
126.1(2)
Cu±P(2)
O(1)±C(1)
O(2)±C(3)
C(1)±C(2)
C(2)±C(3)
C(1)±C(4)
C(3)±C(11)
av.C±F

B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
69
The structure of [Cu(PPh3)2{C7F15C(O)CHC(O)C7F15}]
(Fig.3 ) shows that this compound adopts a distorted
tetrahedral geometry.The structure is not as distorted as
[Cu(PCy3)2(hfacac)] which contains the bulky tricyclohex-
ylphosphine ligand [21], but has a similar P±Cu±P bond
angle to [Cu(PPh3)2(tfac)] (tfac ˆ tri¯uoroacetylacetone;
1278) [22].The Cu±P bond lengths are virtually the same as
those in both [Cu(PPh3)2(ttfac)] (ttfac ˆ 2-thenoyltri¯uor-
oacetone) [23] and [Cu(PCy3)2(hfacac)], and although
the Cu±O bond length is nearly identical to [Cu(PPh3)2(hfa-
Ê
cac)] (2.120 A), the full structural data for this compound
are not available [24].Similar to [Cu{C 6F13C(O)CH-
C(O)C6F13}2(H2O)2], one of the C7F15 chains exhibits
considerable disorder beyond the a-CF2 group and this
static disorder was modelled for the ¯uorine atoms on
C(12), C(13) and C(15) over two sites with 50:50 occu-
pancy and the central carbon atom C(14) which was
similarly modelled over two sites with 50:50 occupancy.
However, this disorder prevented the identi®cation of
genuine short non-bonded FÁÁÁF contacts, even although
¯uorous layers are observed in the solid-state packing
diagram demonstrating the preference for the ¯uorous
ponytails to align.
Fig.3.Molecular structure of [Cu(PPh 3)2{C7F15C(O)CHC(O)C7F15}]
showing part of the atom label scheme with 50% probability ellipsoids.
H atoms are omitted for clarity.One of the C 7F15 chains shows disorder.
3. Conclusions
Dichloromethane, dried by heating to re¯ux over CaH2,
diethyl ether and THF, dried by re¯uxing over sodium
metal, were distilled under nitrogen, stored in closed
ampoules over molecular sieves and freezed/pumped/
thawed three times to remove all the dissolved gases before
Per¯uoroalkylated analogues of 2,4-pentanedione (hfa-
cac), readily prepared by a two step reaction sequence,
undergo straightforward reactions with metal salts to generate
stable per¯uoroalkyl-b-diketonate metal complexes.X-ray
structural determinations reveal tetragonal distorted octahed-
rally coordinated metal centres for [Cu(L±L)2(H2O)2] {L±
L ˆ CF3C(O)CHC(O)C6F13, C6F13C(O)CHC(O)C6F13} and
distorted tetrahedral geometry for [Cu(PPh3)2{C7F15-
C(O)CHC(O)C7F15}].All the three structures possess dis-
ordered per¯uoroalkyl substituents and the disorder has been
modelled for the ®rst time.
use.The [Cu(PPh ) (NO3)] was prepared by the literature
3 2
route [25] whilst dry methanol (Aldrich), methyl magne-
sium bromide (3 mol dmÀ3 in diethyl ether, Aldrich) and
tri¯uoroacetic, per¯uoroheptanoic and per¯uorooctanoic
acids and their ethyl esters (Fluorochem) were used as
supplied.
4.1.1. 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-octan-
2-one [C6F13COCH3]
A solution of per¯uoroheptanoic acid (25 g, 0.069 mol) in
diethyl ether (23 cm3) was added dropwise over 1 h to methyl
magnesium bromide (3.0 mol dmÀ3 solution; 69 cm3,
0.206 mol) in diethyl ether (36 cm3) and the reaction mixture
re¯uxed for 2 h.On cooling, the reaction was quenched with
4. Experimental
4.1. General experimental procedures
ice (62.5 g) followed by hydrochloric acid (6 mol dmÀ3
,
Proton, 13C and 19F NMR spectroscopies were carried out
on a Bruker ARX250 spectrometer at 250.13, 62.90 and
235.34 MHz. All the chemical shifts are quoted in ppm using
63 cm3), the aqueous layer extracted with diethyl ether
(3 Â 30 cm3) and the organic fractions combined.The result-
ing yellow solution was washed with a saturated sodium
chloride solution, dried over magnesium sulfate and the
solvent removed in vacuo to leave a pale yellow slightly
viscous liquid.The product was isolated from the tertiary
alcohol (C6F13C(CH3)2OH) by distillation under vacuum
(23.1 mmHg, 46±49 8C) to give the product as a clear colour-
the high-frequency positive convention; H and 13C NMR
1
spectra were referenced to external SiMe4 and 19F NMR
spectra to external CFCl3.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 Butter-
worth Laboratories Ltd.or the Elemental Analysis Service at
the University of North London.Mass spectra were recorded
on a Kratos concept 1H mass spectrometer.
1
lessliquid.Yield14.75 g,59%. H NMR(CDCl3):d2.45[3H,
4
s, CH3]. 19F{1H} NMR (CDCl3): d À81.44 [3F, t, JFÀF
ˆ
4
9:3 Hz, CF3], À120.90 [2F, t, JFÀF ˆ 12:1 Hz, a-CF2],

70
B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
À122.90[2F, m, CF2], À122.16[2F, m, CF2], À124.09[2F, m,
CF2], À126.74 [2F, m, CF2]. 13C NMR (CDCl3): d 25.36 [s,
n(C±O±H).Analytically calculated for C 10H2O2F16: C, 26. 2;
H, 0.4; F, 66.4. Found: C, 25.9; H, 0.5; F, 66.4.
2
CH3], 105±120 [m's, C6F13], 191.32 [t, JCÀF ˆ 27:1 Hz,
‡
‡
C=O].MS (ES)
[C6F13] (100%), 169 [C3F7] .IR: 1746 cm
m/z: 362 [M ], 361 [M±H] , 319
n(C=O).
4.1.4. 1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,12,
13,13,14,14,15,15,15-Hexacosafluoro-pentadecane-
7,9-dione [C6F13C(O)CH2C(O)C6F13] (2)
‡
‡
À1
Analytically calculated for C8H3OF13: C, 26.5; H, 0.8; F,
68.2. Found: C, 26.8; H, 0.9; F, 68.7.
1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,12,13,13,14,14,
15,15,15-Hexacosa¯uoro-pentadecane-7,9-dione [C6F13C-
(O)CH2C(O)C6F13] (2) was prepared similarly as a colour-
less viscous oil (15 mmHg, 52±55 8C) in 74% yield from
ethyl per¯uoroheptanoate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tri-
4.1.2. 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Pentadecafluoro-
nonan-2-one [C7F15COCH3]
3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Pentadeca¯uoro-nonan-2-one
[C7F15COCH3] was prepared similarly as a clear colourless
liquid(20 mmHg, 55±56 8C)in52%yield. 1H NMR(CDCl3):
d 2.4 [3H, s, CH3]. 19F{1H} NMR (CDCl3): d À81.41 [3F, t,
1
deca¯uoro-octan-2-one. H NMR (CDCl3): d 6.45 [1H, s,
C=C±H], 9.2 [1H, br s, C±OH]. 19F{1H} NMR (CDCl3): d
4
À81.28 [3F, t, JFÀF ˆ 9:6 Hz, CF3], À120.30 [2F, t,
4
4JFÀF ˆ 9:3 Hz, CF3], À120.86 [2F, t, JFÀF ˆ 12:1 Hz, a-
4JFÀF ˆ 13:4 Hz, a-CF2], À122.07 [2F, m, CF2], À122.75
[2F, m, CF2], À123.21 [2F, m, CF2], À126.55 [2F, m, CF2].
13C NMR (d6-acetone): d 98.31 [s, C8], 105 ± 121 [m's,
C6F13], 176.07 [t, 2JCÀF ˆ 27:2 Hz, C7,9].MS (EI) m/z: 708
CF2], À121.94 [2F, m, CF2], À122.56 [2F, m, CF2], À122.80
[2F, m, CF2], À122.84 [2F, m, CF2], À126.69 [2F, m, CF2].
‡
‡
‡
MS (ES) m/z: 413 [MH] , 393 [M±F] , 333 [M±2F]
(100%), 150 [C3F6] , 69 [CF3] .IR: 1765 cm À1 n(C=O).
[M] (trace), 689 [M±F] , 389 [CO(CH2)COC6F12]
‡
‡
‡
‡
‡
‡
‡
‡
(100%), 319 [C6F13] , 169 [C3F7] , 69 [CF3] .IR:
4.1.3. 1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-
Hexadecafluorodecan-2,4-dione
[CF3C(O)CH2C(O)C6F13] (1)
1663 cmÀ1 n(C=O), 1616 cmÀ1 n(C±OH).Analytically cal-
culated for C15H2O2F26: C, 25.4; H, 0.3. Found: C, 25.1; H,
0.4.
A solution of ethyl tri¯uoroacetate (1.64 cm3, 0.0138 mol)
in diethyl ether (5 cm3) was added dropwise to a stirred
solution of sodium ethoxide (1.03 g, 0.0152 mol) in diethyl
ether (20 cm3) at 0 8C, followed by a solution of 3,3,4,4,5,5,
6,6,7,7,8,8,8-trideca¯uorooctan-2-one (5 g, 0.0138 mol) in
diethyl ether (5 cm3) over 1 h.The reaction was maintained
at 0 8C for 12 h, allowed to warm to room temperature
and stirred for a further 48 h.The mixture was hydrolysed
with glacial ethanoic acid (1 g, 0.0166 mol) in water (5 cm3),
before the addition of copper(II) acetate (3.94 g, 0.0197 mol)
in water (22 cm3), which generated an iridescentgreen colour.
The ethereal layer was removed in vacuo, to leave the
insoluble green copper complex in the aqueous layer.The
crystalline solid was ®ltered, washed with ice-cold water
and light petroleum (40±60 8C), and dried under vacuum.
This copper bis(1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-hexadeca-
¯uoro-decane-2,4-dionate) complex was then dissolved in
diethyl ether and hydrogen sulphide gas was passed over
the stirred solution for 25 min, during this time the solution
turned from green to dark black (CuS).The vessel was then
¯ushed with nitrogen for 1 h to remove the excess hydrogen
sulphide.Evaporation of the diethyl ether followed by
vacuum distillation (11.25 mmHg, 48±50 8C) afforded the
products as a pale yellow viscous oil.Yield 20. g, 32%. 1H
NMR(CDCl3):d 6.25[1H, s, C=C±H], 9.95[1H, brs, C±OH].
19F{1H} NMR (CDCl3): d À76.93 [3F, s, a-CF3], À81.29 [3F,
m, terminal CF3], À119.64 [2F, t, 4JFÀF ˆ 11:3 Hz, a-CF2],
À121.26[2F, m, CF2], À122.73[2F, m, CF2], À123.36[2F, m,
CF2], À126.76 [2F, m, CF2]. 13C NMR (CDCl3): d 95.51 [s,
4.1.5. 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,13,13,14,
14,15,15,16,16,17,17,17-Triacontafluoro-heptadecane-
8,10-dione [C7F15C(O)CH2C(O)C7F15] (3)
1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,13,13,14,14,15,
15,16,16,17,17,17-Triaconta¯uoro-heptadecane-8,10-dione
[C7F15C(O)CH2C(O)C7F15] (3) was prepared similarly as a
cream solid (128±130 8C, 20 mmHg) in 30% yield from
ethyl per¯uorooctanoate and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-
pentadeca¯uoro-nonan-2-one. 1H NMR (CDCl3): d 6.45
[1H, s, C=C±H], ꢀ6±9 (position variable) [1H, br s, C±
4
OH]. 19F{1H} NMR (CDCl3): d À80.81 [3F, t, JFÀF
ˆ
4
9:8 Hz, CF3], À120.10 [2F, t, JFÀF ˆ 12:2 Hz, a-CF2],
À121.08 [2F, m, CF2], À121.64 [2F, m, CF2], À122.00
[2F, m, CF2], À122.37 [2F, m, CF2], À125.84 [2F, m, CF2].
13C NMR (CDCl3): d 96.99 [s, C9], 105 ± 121 [m's, C7F15],
‡
2
177.96 [t, JCÀF28:3 Hz, C8,10].MS (ES) m/z: 808 [M]
(100%), 413 [C7F15CO2] , 369 [C7F15] , 169 [C3F7] .IR:
‡
‡
‡
1705, 1696, 1653, 1617 cmÀ1
.
4.1.6. Copper bis(1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,
10-hexadecafluoro-decane-2,4-dionate)
[Cu{CF3C(O)CHC(O)C6F13}2] (4a)
Copper(II) acetate (0.102 g, 5:11 Â 10À4 mol) dissolved in
methanol (10 cm3) was added dropwise to a stirred solution of
sodium acetate (0.084 g, 1:022 Â 10À3 mol) and 1,1,1,5,5,6,
6,7,7,8,8,9,9,10,10,10-hexadeca¯uoro-decane-2,4-dione (1)
(0.468 g, 1:022 Â 10À3 mol) in methanol (10 cm3) and the
reaction mixture stirred for 1 h.The solvent was removed to
yield the product as a pale green powdery solid, which was
washed with hexane and dried in vacuo over silica gel.Yield
0.41 g, 82%. IR: 1636, 1527 cmÀ1.Analytically calculated
for CuC20H2O4F32: C, 24.5; H, 0.2. Found: C, 23.9; H, 0.3.
1
C3], 105 ± 121 [m's, C6F13], 117.45 [q, JCÀF ˆ 281:3 Hz,
2
CF3], 175.83 [q, JCÀF ˆ 38:6 Hz, C2ˆO], 179.53 [t,
‡
2JCÀF ˆ 27:9 Hz, C4=O].MS (ES) m/z: 458 [M] , 457 [M±
‡
‡
H] (100%), 439 [M±F] .IR: 1682 cm À1 n(C=O), 1622 cmÀ1

B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
71
4.1.7. Copper bis(1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11
,11,12,12,13,13,14,14,15,15,15-hexacosafluoro-
pentadecane-7,9-dionate) [Cu{C6F13C(O)
omethane(1:1,30 cm3)andthereactionmixturestirredfor1 h
when a powdery, yellow/orange solid was formed.The com-
plex was isolated by ®ltration, washed with cold THF/dichlor-
omethane and dried in vacuo.Yield 0.326 g, 81.5%. 1H NMR
(CDCl3): d 6.4 [C±H]. 19F{1H} NMR (CDCl3): d À81.31 [3F,
t, 4JFÀF ˆ 9:8 Hz, CF3], À116.76 [2F, t, 4JFÀF ˆ 12:7 Hz, a-
CF2], À121.81 [2F, m, CF2], À122.25 [2F, m, CF2], À123.28
CHC(O)C6F13}2] (4b)
Copper bis(1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,12,
13,13,14,14,15,15,15-hexacosa¯uoro-pentadecane-7,9-dio-
nate) [Cu{C6F13C(O)CHC(O)C6F13}2] (4b) was prepared
similarly, but precipitated out of solution and was ®ltered off
as a ®ne green powder which was dried in vacuo over silica
gel (88% yield).IR: 1635, 1526 cm À1.Analytically calcu-
lated for CuC30H2O4F52: C, 24.4; H, 0.1. Found: C, 24.6; H,
0.2.
[2F, m, CF2], À126À.614 [2F, m, CF2].MS (FAB) m/z: 1517
‡
[M] .IR: 1595 cm
PdC30H2O4F52: C, 23.7; H, 0.1. Found: C, 23.6; H, 0.3.
n(C=O).Analytically calculated for
4.1.11. Palladium bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,
11,11,12,12,13,13,14,14,15,15,16,16,17,17,17-
triacontafluoro-heptadecane-8,10-dionate)
4.1.8. Copper bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,
12,12,13,13,14,14,15,15,16,16,17,17,17-
Triacontafluoro-heptadecane-8,10-dionate)
[Pd{C7F15C(O)CHC(O)C7F15}2] (5c)
Palladium bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,
13,13,14,14,15,15,16,16,17,17,17-triaconta¯uoro-hepta-
decane-8,10-dionate) [Pd{C7F15C(O)CHC(O)C7F15}2] (5c)
was prepared similarly with 82% yield. 19F{1H} NMR
[Cu{C7F15C(O)CHC(O)C7F15}2] (4c)
Copper bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,13,
13,14,14,15,15,16,16,17,17,17-Triaconta¯uoro-heptade-
cane-8,10-dionate) [Cu{C7F15C(O)CHC(O)C7F15}2] (4c)
was prepared similarly, but precipitated out of solution
4
(C6D6): d À81.24 [3F, t, JFÀF ˆ 9:8 Hz, CF3], À117.17
[2F, m, CF2], À121.52 [2F, m, CF2], À121.97 [2F, m, CF2],
À122.40 [2F, m, CF2], À123.13 [2F, m, CF2], À126.57 [2F,
and was ®ltered off as a ®ne green powder which was dried
À1
‡
in vacuo over silica gel (78% yield).IR: 1626, 1528 cm
.
m, CF2].MS (FAB) m/z: 1721 [M] .IR: 1594 cm À1 n(C=O).
Analytically calculated for CuC34H2O4F60: C, 24.3; H, 0.1.
Found: C, 22.4; H, 0.1.
4.1.12. Nickel bis(1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-
hexadecafluoro-decane-2,4-dionate)
4.1.9. Palladium bis(1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-
hexadecafluoro-decane-2,4-dionate)
[Ni{CF3C(O)CHC(O)C6F13}2] (6a)
Nickel dichloride hexahydrate (0.0977 g, 4:11 Â 10À4 mol)
was dissolved in methanol (5 cm3) and added to a stirred
solution of sodium acetate (0.067 g, 8:22 Â 10À4 mol) and
1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-hexadeca¯uoro-decane-2,
4-dione (1) (0.377 g, 8:22 Â 10À4 mol) in methanol (25 cm3).
The reaction mixture was stirred for 1 h and the solvent
removed to give the product as a pale green powdery solid,
which was washed with hexane and dried in vacuo over
[Pd{CF3C(O)CHC(O)C6F13}2] (5a)
Palladium acetate (0.0881 g, 3:92 Â 10À4 mol) was added
to a solution of 1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-hexadeca-
¯uoro-decane-2,4-dione (1) (0.359 g, 7:85 Â 10À4 mol) in
THF and dichloromethane (1:1, 30 cm3) and the reaction
mixture stirred for 1 h.The solvent was removed in vacuo to
yield a thick, black tar from which the product was recrys-
tallised as a powdery yellow solid from re¯uxing toluene and
then dried in vacuo.Yield 0.21 g, 52%. 1H NMR (CDCl3): d
6.4 [C±H]. 19F{1H} NMR (CDCl3): d À73.42 [3F, s, cis/
trans-a-CF3], À73.56 [3F, s, cis/trans-a-CF3], À81.18 [3F, t,
4JFÀF ˆ 11:3 Hz, cis/trans-terminal CF3], À81.32 [3F, t,
4JFÀF ˆ 8:5 Hz, cis/trans-terminal CF3] À116.8 [2  2F,
‡
silica gel.Yield 03. 4 g, 85%.MS (FAB) m/z: 974 [MH] .
IR: 1639, 1527, 1495 cmÀ1.Analytically calculated for
NiC20H2O4F32: C, 24.7; H, 0.1. Found: C, 24.6; H, 0.2.
4.1.13. Nickel bis(1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,
12,13,13,14,14,15,15,15-hexacosafluoro-pentadecane-7,9-
dionate) [Ni{C6F13C(O)CHC(O)C6F13}2] (6b)
4
2 overlapping triplets, JFÀF ˆ 12:7 and 12.8 Hz, a-
CF2's], À121.91 [4F, m, CF2], À122.29 [4F, m, CF2],
À123.30 [4F, m, CF2], À126.60 [4F, m, CF2].MS (FAB)
Nickel bis(1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,12,13,
13,14,14,15,15,15-hexacosa¯uoro-pentadecane-7,9-dionate)
[Ni{C6F13C(O)CHC(O)C6F13}2] (6b) was prepared similarly
as an apple green solid in 92% yield.MS (FAB) m/z: 1472
‡
‡
m/z: 1043 [M ‡ Na] , 1020 [M] .IR: 1598 cm À1 n(C=O).
Analytically calculated for PdC20H2O4F32: C, 23.6; H, 0.2.
Found: C, 22.9; H, 0.2.
‡
‡
‡
[M] , 1153 [M±C6F13] , 319 [C6F13] .IR: 1638, 1528,
1490 cmÀ1.Analytically calculated for NiC 30H2O4F52: C,
24.5; H, 0.1. Found: C, 24.3; H, <0.3.
4.1.10. Palladium bis(1,1,1,2,2,3,3,4,4,5,5,6,6,
10,10,11,11,12,12,13,13,14,14,15,15,15-
hexacosafluoro-pentadecane-7,9-
4.1.14. Nickel bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,
12,12,13,13,14,14,15,15,16,16,17,17,17-
triacontafluoro-heptadecane-8,10-dionate)
dionate) [Pd{C6F13C(O)CHC(O)C6F13}2] (5b)
Palladium acetate (0.0591 g, 2:63 Â 10À4 mol) was added
to a solution of 1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,-11,11,12,
12,13,13,14,14,15,15,15-hexacosa¯uoro-pentadecane-7,9-
dione (2) (0.373 g, 5:26 Â 10À4 mol) in THF and dichlor-
[Ni{C7F15C(O)CHC(O)C7F15}2] (6c)
Nickel bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,13,
13,14,14,15,15,16,16,17,17,17-triaconta¯uoro-hepta-

72
B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
decane-8,10-dionate) [Ni{C7F15C(O)CHC(O)C7F15}2] (6c)
was prepared similarly as an apple green solid in 94%
4.1.18. Copper bis(triphenylphosphine)(1,1,1,2,2,3,3,4,
4,5,5,6,6,10,10,11,11,12,12,13,13,14,14, 15,15,15-
hexacosafluoro-pentadecane-7,9-dionate)
‡
yield.MS (FAB) m/z: 1672 [M] .IR: 1638, 1533, 1499
cmÀ1
.
[Cu(PPh3)2{C6F13C(O)CHC(O)C6F13}] (8a)
Sodium hydroxide (0.0185 g, 3:09 Â 10À4 mol) and 1,1,1,
2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,12,13,13,14,14,15,15,
15-hexacosa¯uoro-pentadecane-7,9-dione (2) (0.219 g,
3:09 Â 10À4 mol) were dissolved in methanol (20 cm3)
and [CuI(PPh3)2NO3] (0.201 g, 3:09 Â 10À4 mol) added.
After stirring for 30 min, the orange precipitate was ®ltered,
washed with methanol and dried in vacuo over silica gel.
Yield: 0.38 g, 95%. 1H NMR (CDCl3): d 5.65 [1H, s, C±H],
7.6 [30H, br s, C6H5]. 19F{1H} NMR (CDCl3): d À81.23
4.1.15. Zinc bis(1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-
hexadecafluoro-decane-2,4-dionate)
[Zn{CF3C(O)CHC(O)C6F13}2] (7a)
Sodiumhydroxide(0.033 g,8:17 Â 10À4 mol)wasaddedto
a stirred solution of 1,1,1,5,5,6,6,7,7,8,8,9,9,10,10,10-hexa-
deca¯uoro-decane-2,4-dione (1) (0.374 g, 8:17 Â 10À4 mol)
in methanol (25 cm3).On complete dissolution, zinc dichlor-
ide (0.0557 g, 4:083 Â 10À4 mol) was added and the reaction
mixturestirredfor2 h.Afterremovingthe solventinvacuothe
product was dried invacuo over silica gel.Yield: 0.34 g, 85%.
1H NMR (CDCl3): d 6.15 [s, C±H]. 19F{1H} NMR (C6D6): d
À76.24 [3F, s, a-CF3], À81.77 [3F, t, 4JFÀF ˆ 10:0 Hz, CF3],
4
4
[3F, t, JFÀF ˆ 9:7 Hz, CF3], À119.91 [2F, t, JFÀF
ˆ
13:0 Hz, a-CF2], À122.20 [2F, m, CF2], À122.80 [2F, m,
CF2], À123.26 [2F, m, CF2], À126.57 [2F, m, CF2]. 31P{1H}
NMR (CDCl3): d À3.2 [br s]. IR: 1646 cmÀ1 n(C=O).
Analytically calculated for CuC51H31O2F26P2: C, 47.3; H,
2.4. Found: C, 47.3; H, 2.4.
4
À120.01 [2F, t, JFÀF ˆ 13:5 Hz, a-CF2], À122.07 [2F, m,
CF2], À122.52 [2F, m, CF2], À123.28 [2F, m, CF2], À126.74
‡
À1
[2F, m, CF2].MS (FAB) m/z: 979 [M] .IR: 1645 cm
n(C=O).
4.1.19. Copper bis(triphenylphosphine)(1,1,1,2,2,3,3,4,4,
5,5,6,6,7,7,11,11,12,12,13,13,14,14,15,15,16,16,17,17,
17-triacontafluoro-heptadecane-8,10-dionate)
4.1.16. Zinc bis(1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,
12,13,13,14,14,15,15,15-hexacosafluoro-pentadecane-
7,9-dionate) [Zn{C6F13C(O)CHC(O)C6F13}2] (7b)
Zinc bis(1,1,1,2,2,3,3,4,4,5,5,6,6,10,10,11,11,12,12,13,
13,14,14,15,15,15-hexacosa¯uoro-pentadecane-7,9-dio-
nate) [Zn{C6F13C(O)CHC(O)C6F13}2] (7b) was prepared
similarly.The white powdery product was ®ltered from
the reaction mixture, washed with methanol and dried in
vacuo over silica gel.Yield: 65%. 1H NMR (CDCl3): d 5.3
[Cu(PPh3)2{C7F15C(O)CHC(O)C7F15}] (8b)
Copper bis(triphenylphosphine)(1,1,1,2,2,3,3,4,4,5,5,6,6,
7,7,11,11,12,12,13,13,14,14,15,15,16,16,17,17,17-triacon-
ta¯uoro-heptadecane-8,10-dionate) [Cu(PPh3)2{C7F15C(O)
CHC(O)C7F15}] (8b) was prepared similarly with 92%
1
yield. H NMR (CDCl3): d 5.91 [1H, s, C±H], 7.4 [30H,
br s, C6H5]. 19F{1H} NMR (CDCl3): d À81.25 [3F, t,
4
4JFÀF ˆ 9:3 Hz, CF3], À119.93 [2F, t, JFÀF ˆ 11:8 Hz,
[s, C±H].19F{1H} NMR (C6D6):
d
À81.80 [3F, t,
a-CF2], À122.00 [2F, m, CF2], À122.50 [2F, m, CF2],
31
4JFÀF ˆ 10:1 Hz, CF3], À120.23 [2F, t, JFÀF ˆ 13:5 Hz,
a-CF2], À122.12 [2F, m, CF2], À122.63 [2F, m, CF2],
À123.29 [2F, m, CF2], À126.73 [2F, m, CF2].MS (FAB)
À122.77 [2F, m, CF2], À123.18 [2F, m, CF2], À126.57
4
[2F, m, CF2]. P{1H} NMR (CDCl3): d À3.4 [br s]. IR:
‡
1646 cmÀ1 n(C=O).MS (FAB) m/z: 1395 [M] .Analyti-
cally calculated for CuC53H31O2F30P2: C, 45.6; H, 2.2.
Found: C, 45.5; H, 2.2.
‡
‡
‡
m/z: 979 [M] , 10À012 [MNa] , 910 [M±CF3] , 69
‡
[CF3] .IR: 1646 cm
for ZnC30H2O4F52: C, 24.4; H, 0.1. Found: C, 23.9; H,
n(C=O).Analytically calculated
<0.3.
4.1.20. Crystal structures of [Cu{CF3C(O)CHC(O)
C6F13}2(H2O)2], [Cu{C6F13C(O)CHC(O)C6F13}2
(H2O)2] and [Cu(PPh3)2(C7F15C(O)CHC(O)C7F15)]
Crystals of (4aÁ2H2O) and (4bÁ2H2O) were grown by slow
evaporation from ether solutions of the complexes over a
layer of chloroform.Crystals of ( 8b) were grown by slow
evaporation from acetone.
4.1.17. Zinc bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,
13,13,14,14,15,15,16,16,17,17,17-triacontafluoro-
heptadecane-8,10-dionate)
[Zn{C7F15C(O)CHC(O)C7F15}2] (7c)
Zinc bis(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,11,11,12,12,13,13,
14,14,15,15,16,16,17,17,17-triaconta¯uoro-heptadecane-
8,10-dionate) [Zn{C7F15C(O)CHC(O)C7F15}2] (7c) was
prepared similarly.The white powdery product was ®ltered
from the reaction mixture, washed with methanol and dried
in vacuo over silica gel.Yield: 79%. 19F{1H} NMR (C6D6):
4.1.21. Crystal data
C20H6CuF32O6 (4aÁ2H2O), M ˆ 1013:78, monoclinic,
Ê
Ê
Ê 3
space group P21/n, a ˆ 13:917(7) A, b ˆ 5:375(3) A,
Ê
c ˆ 20:678(11) A, b ˆ 103:704(8)8, U ˆ 1502:7(13) A
(by least squares re®nement of 2336 re¯ections), T ˆ
150(2) K, graphite-monochromated Mo Ka radiation,
4
d À82.91 [3F, t, JFÀF ˆ 9:5 Hz, CF3], À121.38 [2F, m,
CF2], À122.82 [2F, m, CF2], À123.50 [2F, m, CF2], À124.08
[2F, m, CF2], À124.72 [2F, m, CF2], À127.80 [2F, m, CF2].
l ˆ 0:71073 A, Z ˆ 2, Dc ˆ 2:240 g cmÀ3, Fꢁ0 0 0† ˆ
Ê
MS (FAB) m/z: 1680 [M] , 1660 [M-F,H] .IR: 1642 cm À1
n(C=O).Analytically calculated for ZnC 34H2O4F60: C, 24.3;
H, 0.1. Found: C, 24.3; H, 0.1.
982, dimensions 0:32 mm  0:09 mm  0:08 mm, m (Mo
Ka) ˆ 0.966 mmÀ1, empirical absorption correction, max-
imum and minimum transmission factors of 0.928 and
‡
‡

B. Croxtall et al. / Journal of Fluorine Chemistry 119 (2003) 65±73
73
0.407, respectively (the minimum transmission factor is
smaller than that calculated since the empirical absorption
correction compensates for absorption by the glass mounting
®bre), Bruker APEX 2000 diffractometer, data collection
range l ˆ 1:6±25.08, À16 ꢂ h ꢂ 16, À6 ꢂ k ꢂ 6, À24 ꢂ
l ꢂ 24, no crystal decay was detected; 7865 re¯ections were
measured and 2651 were unique (Rint ˆ 0:0674), ®nal
R1 ˆ 0:0598, wR2 ˆ 0:1518 (0.0810 and 0.1595, respec-
meters.The data were corrected for Lorentz and polarisation
effects.Crystallographic data (excluding structure factors) for
the structures in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary
publication nos.CCDC 192861±192863.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).
tively for all the data) for 277 variables.The ®nal residual
Ê À3
Fourier map showed peaks of 0.766 and ±1.234 eA
.
C30H6CuF52O6 (4bÁ2H2O), M ˆ 1513:89, monoclinic,
Acknowledgements
Ê
Ê
space group P2/c, a ˆ 14:6481(10) A, b ˆ 5:5300(4) A,
Ê
Ê 3
c ˆ 28:947(2) A, b ˆ 95:093(1)8, U ˆ 2335:5(3) A (by
least squares re®nement of 5604 re¯ections), T ˆ
160(2) K, graphite-monochromated Mo Ka radiation,
We would like to thank the Royal Society (EGH, AMS),
the EPSRC (BC) and GlaxoSmithKline (BC) for ®nancial
support.
l ˆ 0:71073 A, Z ˆ 2, Dc ˆ 2:153 g cmÀ3, Fꢁ0 0 0† ˆ
Ê
1462, dimensions 0:30 mm  0:14 mm  0:12 mm, m (Mo
Ka) ˆ 0.719 mmÀ1, empirical absorption correction, max-
imum and minimum transmission factors of 0.93 and 0.83,
respectively, Bruker APEX 2000 diffractometer, data col-
lection range y ˆ 1:4±26.08, À18 ꢂ h ꢂ 18, À6 ꢂ k ꢂ 6,
À35 ꢂ l ꢂ 35, no crystal decay was detected, 17270 re¯ec-
tions were measured and 4591 were unique (Rint ˆ 0:0237),
®nal R1 ˆ 0:0453, wR2 ˆ 0:1214 (0.0568 and 0.1281, res-
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 Â
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pectively for all the data) for 565 variables.The ®nal residual
Ê À3
Fourier map showed peaks of 0.697 and ±0.357 eA
.
Â
[6] I.T. Horvath, Acc.Chem.Res.31 (1998) 641.
C53H31CuF30O2P2 (8b), M ˆ 1395:26, monoclinic, space
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(1999) 183.
Ê
Ê
group C2/c, a ˆ 36:773(2) A, b ˆ 13:222(1) A, c ˆ 22:532
Ê
Ê 3
(1) A, b ˆ 93:729(1)8, U ˆ 10932:0(8) A (by least squares
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37.
re®nement of 12843 re¯ections), T ˆ 150(2) K, graphite-
Ê
monochromated Mo Ka radiation, l ˆ 0:71073 A, Z ˆ 8,
[9] E.G. Hope, A.M. Stuart, J. Fluorine Chem. 100 (1999) 75.
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Trans.(1998) 3765.
Dc ˆ 1:695 g cmÀ3,Fꢁ0 0 0† ˆ 5552,dimensions0:32 mmÂ
0:29 mm  0:15 mm, m (Mo Ka) ˆ 0.603 mmÀ1, empirical
absorption correction, maximum and minimum transmis-
sion factors of 0.746 and 0.655, respectively, Bruker APEX
2000 diffractometer, data collection range y ˆ 1:6±25.08,
À42 ꢂ h ꢂ 43, À15 ꢂ k ꢂ 15, À26 ꢂ l ꢂ 26, no crystal
decay was detected; 38861 re¯ections were measured and
9618 were unique (Rint ˆ 0:028), ®nal R1 ˆ 0:0515,
wR2 ˆ 0:135 (0.0619 and 0.142, respectively, for all the
data) for 862 variables.The ®nal residual Fourier map
[14] E.G. Hope, R.D.W. Kemmitt, D.R. Paige, A.M. Stuart, D.R.W.
Wood, Polyhedron 18 (1999) 2913.
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[16] B. Croxtall, J. Fawcett, E.G. Hope, A.M. Stuart, J. Chem. Soc.,
Dalton Trans.(2002) 491.
Ê À3
0
Ê
showed peaks of 1.13 (0.92 A from C14 ) and À0.60 eA
.
[17] D.J. Adams, D. Gudmunsen, J. Fawcett, E.G. Hope, A.M. Stuart,
Tetrahedron 58 (2002) 3827.
4.1.22. Structure solution and refinement
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E.T. Eisenbraun, B. Zheng, A.E. Kaloyeros, J. Coord. Chem. 38
(1996) 319.
Structure solution by Patterson methods and structure
re®nement on F2 employed SHELXTL/PC Version 5.0
[26].The C±H hydrogen atoms were included in calculated
Ê
positions (C±H ˆ 0:96 A) with isotropic displacement para-
[21] H.-K. Shin, M.J. Hampden-Smith, E.N. Duesler, T.T. Kodas, Can. J.
Chem.70 (1992) 2954.
meters set to 1.2 Ueq of the bonded atom.The aqua hydrogen
atoms of (4aÁ2H2O) and (4bÁ2H2O) were located from dif-
ference Fourier maps and included in re®nement cycles riding
on the oxygen atoms with isotropic displacement parameters
set to 1.5 Ueq of the oxygen atoms.The ¯uorine atoms of the
disordered tri¯uoromethyl groups in (4aÁ2H2O) were re®ned
with isotropic displacement parameters.All other non-hydro-
gen atoms were re®ned with anisotropic displacement para-
[22] M.Bartlett, J.Palenik, Acta Crystallogr.Sect.A 25 (1969) s173.
[23] R.-N. Yang, D.-M. Wang, Y.-F. Liu, D.-M. Jin, Polyhedron 20 (2001)
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(1971) 761.
[25] F.A. Cotton, D.M.L. Goodgame, J. Chem. Soc. (1960) 5267.
[26] G.M. Sheldrick, SHELXTL/PC Version 5.0, Madison, Siemens
Analytical Instruments, WI, USA, 1996.