(Phosphine)gold(I) trifluoromethanesulfonates, trifluoroacetates and trichlorothioacetates

Article abstract of DOI:10.1039/a809714c

Stable, crystalline (phosphine)gold(I) trifluoroacetates of the type (R₃P)AuOC(O)CF₃ have been prepared in high yield from the corresponding chloro complexes with AgOC(O)CF₃ in tetrahydrofuran for R = Me, Ph or o-Tol. The crystal structure of (Me₃P)AuOC(O)CF₃ features trimers with two short aurophilic Au...Au contacts in an angular Au...Au...Au unit. Trichlorothioacetic acid has been aurated (in high yield) using {[(R₃P)Au]₃O}⁺BF₄^- and NaBF₄ in dichloromethane to give equally stable compounds (R₃P)AuSC(O)CCl₃ with R = Me, Ph or o-Tol. In these products the trichlorothioacetate group is exclusively sulfur bonded to the gold atom. The methyl and o-tolyl compounds are dimers in the solid state, but association is based on only very long intermolecular Au...S and Au...Cl contacts, respectively. (Triphenylphosphine)gold thioacetate was prepared similarly, but the product is thermally unstable in both the solid and solution state. It thus appears that the presence of the halogen substituents is essential for the stability of the present compounds, which are useful aurating agents and can be employed for the controlled deposition of gold. [Tri(o-tolyl)phosphine]gold chloride was converted into the trifluoromethanesulfonate (triflate) in 95% yield by treatment with AgOS(O)₂CF₃ in tetrahydrofuran. The crystal structure determination of the CH₂Cl₂ solvate revealed non-ionic, molecular components [Au-O 2.110(3) A, S-O-Au 120.4(2)°], which are associated into dimers via hydrogen bonds [O...H-C 170.2°, C-H 0.969 A, H...O 2.575 A] with two CH₂Cl₂ molecules.

Full text of DOI:10.1039/a809714c

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(Phosphine)gold(I) trifluoromethanesulfonates, trifluoroacetates
and trichlorothioacetates†
Max Preisenberger, Annette Schier and Hubert Schmidbaur*
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4,
D-85747 Garching, Germany
Received 14th December 1998, Accepted 16th March 1999
Stable, crystalline (phosphine)gold() trifluoroacetates of the type (R3P)AuOC(O)CF3 have been prepared in high
yield from the corresponding chloro complexes with AgOC(O)CF3 in tetrahydrofuran for R = Me, Ph or o-Tol.
The crystal structure of (Me3P)AuOC(O)CF3 features trimers with two short aurophilic Au ؒ ؒ ؒ Au contacts in an
angular Au ؒ ؒ ؒ Au ؒ ؒ ؒ Au unit. Trichlorothioacetic acid has been aurated (in high yield) using {[(R3P)Au]3O}ϩBF4
Ϫ
and NaBF4 in dichloromethane to give equally stable compounds (R3P)AuSC(O)CCl3 with R = Me, Ph or o-Tol. In
these products the trichlorothioacetate group is exclusively sulfur bonded to the gold atom. The methyl and o-tolyl
compounds are dimers in the solid state, but association is based on only very long intermolecular Au ؒ ؒ ؒ S and
Au ؒ ؒ ؒ Cl contacts, respectively. (Triphenylphosphine)gold thioacetate was prepared similarly, but the product is
thermally unstable in both the solid and solution state. It thus appears that the presence of the halogen substituents
is essential for the stability of the present compounds, which are useful aurating agents and can be employed for the
controlled deposition of gold. [Tri(o-tolyl)phosphine]gold chloride was converted into the trifluoromethanesulfonate
(triflate) in 95% yield by treatment with AgOS(O)2CF3 in tetrahydrofuran. The crystal structure determination of the
CH2Cl2 solvate revealed non-ionic, molecular components [Au–O 2.110(3) Å, S–O–Au 120.4(2)Њ], which are
associated into dimers via hydrogen bonds [O ؒ ؒ ؒ H–C 170.2Њ, C–H 0.969 Å, H ؒ ؒ ؒ O 2.575 Å] with two CH2Cl2
molecules.
Introduction
Results and discussion
(Phosphine)gold() complexes (R3P)AuX are among the key
reagents in gold chemistry. Apart from the conventional halide
and pseudohalide compounds (X = Cl, Br, I, CN or SCN),1–4
which have been used most extensively in the past, more recent
work has also included several new reagents. Prominent
examples are oxonium salts [(R3P)Au]3OϩXϪ,5 but alkoxides,6
siloxides,7,8 and aryl oxides9–11 of the general type (R3P)AuOR
are also of increasing importance. There is generally a need for
(R3P)AuX complexes with X representing a good leaving group
(a poor donor and nucleophile). With these counter ions, the
cationic agents [(R3P)Au]ϩ can perform as extremely strong
electrophiles as required in most “auration” reactions, includ-
ing applications in homogeneous catalysis.12,13 However, some
of the ideal candidates (R3P)AuX with X = fluoride, tetrafluoro-
borate, hexafluorophosphate or trifluoromethanesulfonate
(triflate) are of very limited stability.14 They often cannot be
isolated and have to be handled in solution at low temperature.
In this context we have resumed investigations of the tri-
fluoromethanesulfonates, trihalogenocarboxylates and thio-
carboxylates, which have not been studied much in the past.15–17
Complexes of this family may have many advantages owing to
their higher thermal stability and good solubility in acceptable
solvents. There is also reason to expect that the compounds
follow a clean thermal decomposition pattern involving decarb-
oxylation as the initial step under mild conditions. This could
offer advantages for gold deposition processes from solution or
even from the vapour.18
Preparation and characterization of the compounds
The trifluoroacetates are readily prepared from (phosphine)-
gold halides and silver trifluoroacetate [eqn. (1)]. For the
(R3P)AuCl ϩ AgOC(O)CF3 →
AgCl ϩ (R3P)AuOC(O)CF3 (1)
1: R = Me
2: R = Ph
3: R = o-Tol
auration of trichlorothioacetic acid, tris[(phosphine)gold] oxo-
nium salts (in the presence of an excess of NaBF4 as counter
ion supplier) have been used [eqn. (2)]. The products can be
{[(R3P)Au]3O}ϩBF4Ϫ ϩ 3 Cl3CC(O)SH →
3 (R3P)AuSC(O)CCl3 ϩ H2O ϩ HBF4 (2)
4: R = Me
5: R = Ph
6: R = o-Tol
isolated in high yields as colourless, crystalline materials, read-
ily soluble in most common polar organic solvents (di- and tri-
chloromethane, tetrahydrofuran), but insoluble in pentane or
diethyl ether. The composition was confirmed by elemental
analysis, mass spectrometry and NMR spectroscopy (Experi-
mental section). It is interesting that for almost all complexes
the most prominent peak in the mass spectra is the [(R3P)Au]ϩ
adduct of the parent compound. Cations of the formula
{CX3CO2[Au(PR3)]2}ϩ appear to be highly favoured upon ion-
ization under high vacuum conditions.
In the scattered literature about previous work in this
area there are several prototypes with simple carboxylate
ligands,19–25 but no more systematic investigations have been
carried out.17
In an exploratory experiment, thioacetic acid has also been
subjected to auration with trigold oxonium tetrafluoroborate
under similar conditions to give (Ph3P)AuSC(O)CH3 7. This
product has much lower thermal stability as compared to the
† Dedicated to Professor Helmut Werner on the occasion of his 65th
birthday.
J. Chem. Soc., Dalton Trans., 1999, 1645–1650
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Fig. 2 Chain formation of the trimers of compound 1 through
Au ؒ ؒ ؒ Au contacts [Au(3) ؒ ؒ ؒ Au(2Ј) 4.322(6) Å].
Fig. 1 Molecular structure of compound 1 (ORTEP26 drawing with
50% probability ellipsoids, H atoms omitted for clarity). Selected bond
lengths [Å] and angles [Њ]: Au(1)–O(11) 2.057(14), Au(1)–P(1) 2.204(5),
O(11)–Au(1)–P(1) 177.0(5), C(11)–O(11)–Au(1) 118.5(13); Au(2)–
O(21) 2.09(2), Au(2)–P(2) 2.217(5), O(21)–Au(2)–P(2) 168.9(5), C(21)–
O(21)–Au(2) 124(2); Au(3)–O(31) 2.08(2), Au(3)–P(3) 2.214(5), O(31)–
Au(3)–P(3) 178.9(5), C(31)–O(31)–Au(3) 121(2); Au(1) ؒ ؒ ؒ Au(2)
3.3136(13), Au(1) ؒ ؒ ؒ Au(3) 3.3326(13), Au(2) ؒ ؒ ؒ Au(1) ؒ ؒ ؒ Au(3)
129.81(3), O(11)–Au(1) ؒ ؒ ؒ Au(2) 81.5(4), O(11)–Au(1) ؒ ؒ ؒ Au(3)
92.1(4), O(21)–Au(2) ؒ ؒ ؒ Au(1) 92.4(6), O(31)–Au(3) ؒ ؒ ؒ Au(1) 75.3(5),
P(1)–Au(1) ؒ ؒ ؒ Au(2) 95.73(14), P(1)–Au(1) ؒ ؒ ؒ Au(3) 90.6(2), P(2)–
Au(2) ؒ ؒ ؒ Au(1) 96.28(14), P(3)–Au(3) ؒ ؒ ؒ Au(1) 103.6(2).
Fig. 3 Cell plot of compound 1 with the chains running along the
x axis.
trichlorothioacetate. It must be handled in solution at temper-
atures well below 0 ЊC to avoid rapid decomposition.
(Triphenylphosphine)- and [tri(o-tolyl)phosphine]-gold tri-
flate 8 and 9 are prepared from the corresponding chlorides by
treatment with AgOS(O)2CF3 in tetrahydrofuran, eqn. (3). The
(R3P)AuCl ϩ AgOS(O)2CF3 →
AgCl ϩ (R3P)AuOS(O)2CF3 (3)
8: R = Ph
9: R = o-Tol
solutions obtained after filtration from the AgCl precipitate are
stable at ambient temperature in the dark, but 8 readily
decomposes upon evaporation of the solvent. Colourless, solid
residues can be kept below Ϫ20 ЊC for some time, however,
especially so if the thf is not removed completely. The o-tolyl
homologue 9 is more robust and the solution and the solid are
stable at temperatures below 0 ЊC. Single crystals of a 9ؒCH2Cl2
solvate are obtained from dichloromethane–pentane at 0 ЊC.
Fig. 4 Molecular structure of compound 4 (ORTEP26 drawing with
50% probability ellipsoids, H atoms omitted for clarity). Selected bond
lengths [Å] and angles [Њ]: Au–P 2.248(4), Au–S 2.315(4); P–Au–S
176.0(2), Au–S–C(2) 101.7(5).
Crystal and molecular structures
Crystals of (trimethylphosphine)gold trifluoroacetate 1, mp
118 ЊC, from tetrahydrofuran–pentane are monoclinic (space
group P21/n, Z = 12, at Ϫ78 ЊC). The asymmetric unit contains
three crystallographically independent molecules. These three
molecules [with the gold atoms Au(1), Au(2) and Au(3), Fig. 1],
are associated into a trimer via two short aurophilic Au ؒ ؒ ؒ Au
contacts: Au(1) ؒ ؒ ؒ Au(2) 3.3136(13) Å, Au(1) ؒ ؒ ؒ Au(3)
3.3326(13) Å, Au(2) ؒ ؒ ؒ Au(1) ؒ ؒ ؒ Au(3) 129.81(3)Њ. These tri-
mers are part of a spiral chain of molecules running along the
x-axis of the crystal (Figs. 2, 3). However, the Au ؒ ؒ ؒ Au con-
tacts between the trimers are much longer and well in excess of
the sum of the van der Waals radii [Au(3) ؒ ؒ ؒ Au(2Ј) 4.322(6) Å].
The individual monomers have a linear configuration at the
gold atoms with angles O–Au–P all close to 180Њ (caption to
Fig. 1), while the angles O–Au–Au and P–Au–Au range from
75.3 to 103.6Њ. These pattern details are rather common in
aggregates of linear gold() complexes L–Au–X, as is the
“crossed swords” arrangement of neighbouring P–Au–O units
(Figs. 1–3). The internal dimensions of the tertiary phosphine
and the trifluoroacetate groups are not unusual and mutually
consistent for the three monomers.
The Au–O bond lengths are in the narrow range from 2.06(1)
to 2.09(2) Å with angles Au–O–C between 119(1) and 124(2)Њ.
The former are to be considered rather long and may indicate
the poor donor properties of the trifluoroacetate group as com-
pared e.g. with the trimethylsiloxide group in (R3P)AuOSiR3
molecules.7,8
Crystals of (trimethylphosphine)gold trichlorothioacetate 4,
mp 143 ЊC, from dichloromethane–diethyl ether, are also mono-
clinic (space group P21/c, Z = 4, at Ϫ110 ЊC), but the lattice is
composed of dimers, the monomeric units of which are related
by a crystallographically imposed centre of inversion (Figs. 4
and 5). In the monomer the gold atom is attached to the sulfur
atom of the trichlorothioacetate group with a rather long
Au–S distance of 2.315(4) Å, but a narrow angle Au–S–C of
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J. Chem. Soc., Dalton Trans., 1999, 1645–1650

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Fig. 7 Molecular structure of compound 9 (ORTEP26 drawing with
50% probability ellipsoids, H atoms omitted for clarity). Selected bond
lengths [Å] and angles [Њ]: Au–P 2.225(1), Au–O(1) 2.110(3), S–O(1)
1.470(3), S–O(2) 1.432(4), S–O(3) 1.426(3), S–C(1) 1.823(5), C(1)–F(1)
1.330(6), C(1)–F(2) 1.319(6), C(1)–F(3) 1.322(6); P–Au–O(1) 176.50(8),
Au–O(1)–S 120.4(2), O(1)–S–O(2) 113.0(2), O(1)–S–O(3) 112.2(2),
O(1)–S–C(1) 101.8(2), O(2)–S–O(3) 118.9(2), O(2)–S–C(1) 104.7(2),
O(3)–S–C(1) 103.9(2), S–C(1)–F(1) 111.0(3), S–C(1)–F(2) 110.4(4), S–
C(1)–F(3) 111.6(4), F(1)–C(1)–F(2) 108.0(5), F(1)–C(1)–F(3) 107.5(4),
F(2)–C(1)–F(3) 108.1(4).
Fig. 5 Association of monomers of compound 4 into dimers, based
on weak Au ؒ ؒ ؒ AuЈ [4.012 Å] and Au ؒ ؒ ؒ SЈ [3.722 Å] contacts.
Fig. 8 Hydrogen bonding between compound 9 and the CH2Cl2
solvent molecules [C–H(1) 0.969 Å, H(1) ؒ ؒ ؒ O(3Ј) 2.575 Å;
C–H(1) ؒ ؒ ؒ O(3Ј) 170.2Њ; C–H(2) 0.964 Å, H(2) ؒ ؒ ؒ O(3) 2.556 Å;
C–H(2) ؒ ؒ ؒ O(3) 142.9Њ].
Fig. 6 Dimeric structure of compound 6 (ORTEP26 drawing with 50%
probability ellipsoids, H atoms omitted for clarity). Selected bond
lengths [Å] and angles [Њ]: Au–P 2.2722(13), Au–S 2.3104(13); P–Au–S
173.34(4), C(1)–S–Au 104.1(2), Au ؒ ؒ ؒ Cl(2Ј) 3.720(1).
101.7(5)Њ. It should be noted that the O and Au atoms are not
drawn together: The S–Au–P axis is close to linear [176.0(2)Њ]
and the small deviation from 180Њ is in the opposite direction.
The internal geometry of the phosphine and the SC(O)CCl3
ligands is not exceptional.
Surprisingly, the intermolecular bonding is not based on
Au ؒ ؒ ؒ Au interactions, but rather on Au–SЈ contacts: Au ؒ ؒ ؒ
AuЈ 4.012; Au ؒ ؒ ؒ SЈ 3.722 Å. These values are in the range
of van der Waals distances and are probably associated with
only very weak forces. A similar rhomboid array of atoms
(AuSAuЈSЈ, Fig. 5) has recently also been detected in the struc-
ture of gold() thiophosph(in)ate complexes.27,28 However weak,
these interactions are still determining quite significantly the
organization of molecules in the crystal.
Crystals of [tri(o-tolyl)phosphine]gold trichlorothioacetate 6,
mp 154 ЊC, from dichloromethane–diethyl ether are also mono-
clinic (space group P21/n, Z = 4, at Ϫ79 ЊC). The lattice
contains equivalent molecules loosely aggregated to give cen-
trosymmetrical dimers (Fig. 6). The intermolecular forces are
only based on long Cl ؒ ؒ ؒ Au contacts (3.720 Å). As in 4
(above) the trichlorothioacetate unit is attached to the gold
atom via the sulfur atom with an Au–S distance of 2.3104(13)
Å and angles C–S–Au 104.1(2) and P–Au–S 173.34(4)Њ.
The former is wider than in 4, probably owing to the steric
congestion arising through the bulky tri(o-tolyl)phosphine
ligand. Both this distortion and the bending at Au rule out any
intramolecular O ؒ ؒ ؒ Au contacts. However, the P–Au–S bend-
ing is in favour of the intermolecular Cl ؒ ؒ ؒ Au contact which
is similar to the observations made recently for Cl3Ge–Au–
P(o-Tol)3.29
Crystals of compound 9ؒCH2Cl2 are triclinic (space group
¯
P1, Z = 2, at Ϫ80 ЊC). The asymmetric unit contains one
monomer 9 and one solvent molecule (Fig. 7). These com-
ponents are associated into dimeric units via weak hydrogen
bonds as drawn in Fig. 8.30 The two complexes and the two
solvent molecules are related by a crystallographic centre of
inversion.
The configuration at the gold atom is close to linear
[P–Au–O(1) 176.50(8)Њ]. The triflate anion is strongly co-
ordinated to the gold atom via one oxygen atom [O(1)] as
witnessed by a short Au–O contact of only 2.110(3) Å and by a
lengthening of the S–O(1) bond to 1.470(3) Å as compared to
S–O(2) and S–O(3) with 1.432(4) and 1.426(3) Å, respectively.
The angle at the oxygen atom O(1) [120.4(2)Њ] is rather small
and also indicative of covalent Au–O bonding. The geometry
of the CF3SO3 and Ph3P moieties is otherwise unexceptional.
In the structural chemistry of gold there is only one
precedent for gold–triflate bonding:31 dimethylgold() triflate
hydrate contains a CF3SO3 unit bound to gold() unidentately
with an Au–O contact of 2.201(6) Å and an Au–O–S angle of
128.7(4)Њ. The S–O bonds show only small variations [1.456(6)
versus 2 × 1.439(4) Å] suggesting a weaker bonding than in
9. Fully ionic triflate anions have S–O bond lengths smaller
than 1.420 Å, as recently measured for the gold compound
2ϩ
(CH2)2[PPh2SAu(PPh3)]2 2 (CF3SO3Ϫ), where no Au–O con-
tact is discernible.32
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vacuo to leave a volume of 5 ml. Addition of diethyl ether led to
the precipitation of 142 mg (88%) of complex 4 as a white solid.
The compound is air-stable and stable in solution, soluble in
dichloromethane and chloroform, but insoluble in pentane and
diethyl ether. Colourless crystals suitable for X-ray analysis
could be obtained from dichloromethane solution by layering
with diethyl ether, mp 143 ЊC (decomp.) (Found: C, 13.19;
H, 2.30; S, 7.00. C5H9AuCl3OPS requires C, 13.30; H, 2.01;
S, 7.10%). NMR (CDCl3): 1H, δ 1.71 [d, J(HP) 9 Hz, Me]; 13C-
{1H}, δ 101.6 (s, CCl3), 192.9 [s, C(O)S] and 15.1 [d, J(CP) 36
Hz, Me]; 31P-{1H}, δ Ϫ2.0 (s). FAB mass spectrum: m/z 451
(4%, [M ϩ 1]ϩ).
Conclusion
The present study has shown that (phosphine)gold() tri-
halogeno(thio)acetates are readily available from standard
reagents as stable compounds, which are easy to handle owing
to their good solubility. They are a useful addition to the
arsenals of aurating agents and of precursors for gold
deposition processes. Work following up these opportunities is
in progress.
Experimental
General
(Ph3P)AuSC(O)CCl3 5. The synthesis was analogous to that
The experiments were routinely carried out in an atmosphere of
dry and pure nitrogen. Standard equipment was used through-
out. Glassware and solvents were purified, dried and filled/
saturated with nitrogen. Starting materials were either com-
mercially available or synthesized via published procedures:
Ϫ
of compound 4 with {[(Ph3P)Au]3O}ϩBF4 (114 mg, 0.08
mmol), NaBF4 (100 mg, 0.91 mmol) and Cl3CC(O)SH (26 µl,
0.23 mmol) to give 137 mg (93%) of 5. Stability and solubility
as for 4, mp 161 ЊC (decomp.) (Found: C, 37.91; H, 2.49; S, 4.88.
C20H15AuCl3OPS requires C, 37.67; H, 2.37; S, 5.03%). NMR
Ϫ 5
Ϫ 33
{[(Ph3P)Au]3O}ϩBF4
,
{[(Me3P)Au]3O}ϩBF4
,
{[(o-Tol)3-
1
(CDCl3): H, δ 7.35–7.77 (m, Ph); 13C-{1H}, δ 101.4 (s, CCl3),
Ϫ 34
PAu]3O}ϩBF4
,
(Ph3P)AuCl,35 (Me3P)AuCl,33 (o-Tol)3-
PAuCl,36 Cl3CC(O)SH.37
193.8 [s, C(O)S], 134.0 [d, J(CP) 16], 131.7 [d, J(CP) 3], 129.1 [d,
J(CP) 12] and 128.6 [d, J(CP) 63 Hz] (ortho-, para-, meta-, ipso-
C of Ph); 31P-{1H}, δ 37.9 (s). FAB mass spectrum: m/z 637 (7%,
[M ϩ 1]ϩ).
Syntheses
(Me3P)AuOC(O)CF3 1. To a solution of (Me3P)AuCl (120
mg, 0.39 mmol) in thf (30 ml) was added AgOC(O)CF3 (86 mg,
0.39 mmol) dissolved in thf (20 ml). After stirring for 1 h the
reaction mixture was filtered. Evaporation of the solvent from
the filtrate in vacuo to leave a volume of ca. 5 ml and addition of
pentane led to the precipitation of 135 mg (90%) of complex 1
as a white solid. The compound is air-stable as a solid and in
solution, soluble in dichloromethane and tetrahydrofuran, but
insoluble in pentane and diethyl ether. Colourless crystals suit-
able for X-ray analysis could be obtained from tetrahydrofuran
solution by layering with pentane, mp 118 ЊC (decomp.)
(Found: C, 15.28; H, 2.17. C5H9AuF3O2P requires C, 15.56; H,
2.35%). NMR (CDCl3): 1H, δ 1.69 [d, J(HP) 10 Hz, Me];
13C-{1H}, δ 119.3 [q, J(CF) 297, CF3], 158.5 [q, J(CF) 44, CO2]
and 14.7 [d, J(CP) 38 Hz, Me]; 31P-{1H}, δ Ϫ15.3 (s). FAB mass
spectrum: m/z 658 (11%, [M ϩ AuPMe3]ϩ).
(o-Tol)3PAuSC(O)CCl3 6. The synthesis was analogous to
Ϫ
that of compound 4 with {[(o-Tol)3PAu]3O}ϩBF4 (167 mg,
0.10 mmol), NaBF4 (100 mg, 0.91 mmol) and Cl3CC(O)SH (35
µl, 0.31 mmol) to give 203 mg (96%) of 6. Stability and solubil-
ity as for 4. Colourless crystals suitable for X-ray analysis could
be obtained from dichloromethane solution by layering with
diethyl ether, mp 154 ЊC (decomp.) (Found: C, 40.60; H, 3.13.
C23H21AuCl3OPS requires C, 40.64; H, 3.11%). NMR (CDCl3):
1H, δ 6.91–7.88 (m, 12 H, C6H4) and 2.61 (s, 9 H, Me); 13C-{1H},
δ 100.4 (s, CCl3), 193.5 [s, C(O)S], 142.8 [d, J(CP) 12, C2], 133.3
[d, J(CP) 9, C6], 132.1 [d, J(CP) 9, C3], 131.7 [d, J(CP) 2, C4],
126.6 [d, J(CP) 10, C5], 125.0 [d, J(CP) 58, C1] and 22.7 [d,
J(CP) 11 Hz, Me]; 31P-{1H}, δ 16.1 (s). FAB mass spectrum: m/z
679 (3%, [M ϩ 1]ϩ).
(Ph3P)AuSC(O)CH3 7. To a solution of CH3C(O)SH (40 µl,
0.53 mmol) in thf (10 ml) was added slowly at Ϫ30 ЊC a solu-
tion of {[(Ph3P)Au]3O}ϩBF4Ϫ (260 mg, 0.18 mmol) in dichloro-
methane (20 ml), followed by NaBF4 (100 mg, 0.91 mmol).
After stirring for 2 h at Ϫ30 ЊC the solution was filtered. Evap-
oration of the solvent from the filtrate in vacuo at Ϫ20 ЊC to
leave a volume of ca. 5 ml and addition of pentane led to the
precipitation of 231 mg (82%) of complex 7 as a white solid.
The complex decomposes at 0 ЊC and is stable in solution
only below Ϫ30 ЊC (Found: C, 45.41; H, 3.78. C20H18AuOPS
requires C, 44.95; H, 3.40%). NMR (CD2Cl2, Ϫ30 ЊC): 1H,
δ 7.17–7.69 (m, Ph) and 2.51 (s, Me); 13C-{1H}, δ 186.8 [s,
C(O)S], 134.0 [d, J(CP) 14], 131.5 [d, J(CP) 2], 129.0 [d, J(CP)
12] and 128.9 [d, J(CP) 58 Hz] (ortho-, para-, meta-, ipso-C of
Ph); 31P-{1H}, δ 37.9 (s).
(Ph3P)AuOC(O)CF3 2. The synthesis was analogous to
that of complex 1 with (Ph3P)AuCl (120 mg, 0.24 mmol) and
AgOC(O)CF3 (54 mg, 0.24 mmol) to give 131 mg (94%) of 2.
Stability and solubility as for 1, mp 128 ЊC (decomp.) (Found:
C, 41.78; H, 2.80. C20H15AuF3O2P requires C, 41.98; H, 2.64%).
1
NMR (CDCl3): H, δ 7.28–7.81 (m, Ph); 13C-{1H}, δ 119.7 [q,
J(CF) 293, CF3], 164.2 [q, J(CF) 48, CO2], 133.9 [d, J(CP) 13],
132.0 [d, J(CP) 3], 129.1 [d, J(CP) 12] and 127.8 [d, J(CP) 59
Hz] (ortho-, para-, meta-, ipso-C of Ph); 31P-{1H}, δ 27.5 (s).
FAB mass spectrum: m/z 1031 (5%, [M ϩ AuPPh3]ϩ).
(o-Tol)3PAuOC(O)CF3 3. The synthesis was analogous to
that of complex 1 with (o-Tol)3PAuCl (170 mg, 0.32 mmol) and
AgOC(O)CF3 (70 mg, 0.32 mmol) to give 177 mg (91%) of 3.
Stability and solubility as for 1, mp 136 ЊC (decomp.) (Found:
C, 44.85; H, 3.47. C23H21AuF3O2P requires C, 44.97; H, 3.45%).
NMR (CDCl3): 1H, δ 6.84–7.71 (m, 12 H, C6H4) and 2.58 (s, 9
H, Me); 13C-{1H}, δ 118.2 [q, J(CF) 290, CF3], 161.0 [q, J(CF)
47, CO2], 142.8 [d, J(CP) 11, C2], 133.2 [d, J(CP) 10, C6], 132.3
[d, J(CP) 3, C3], 132.0 [d, J(CP) 2, C4], 126.5 [d, J(CP) 10, C5],
123.9 [d, J(CP) 66, C1] and 22.6 [d, J(CP) 11 Hz, Me]; 31P-{1H},
δ 0.4 (s). FAB mass spectrum: m/z: 1115 (4%, [M ϩ AuP-
(o-Tol)3]ϩ).
(Ph3P)AuOS(O)2CF3 8. A solution of (Ph3P)AuCl (372 mg,
0.75 mmol) in 100 ml of thf was treated with a solution of
AgOS(O)2CF3 (192 mg, 0.75 mmol) in 30 ml of the same
solvent. The precipitate of AgCl formed was separated by
filtration. The solvent was removed from the filtrate in a
vacuum at Ϫ20 ЊC. The colourless, flaky residue decomposes
above Ϫ20 ЊC; yield 456 mg (100%). NMR (CDCl3, Ϫ20 ЊC):
1H, δ 7.58–7.45 (m, Ph); 13C-{1H}, δ 134.0 [d, J(CP) 14,
C2/6)], 132.7 [d, J(CP) 3, C4], 129.5 [d, J(CP) 12, C3/5], 127.0
[d, J(CP) 68, C1] and 120.3 [q, J(CF) 317 Hz, CF3]; 31P-{1H},
δ 28.1 (s).
(Me3P)AuSC(O)CCl3 4. To a solution of Cl3CC(O)SH (40 µl,
0.36 mmol) in dichloromethane (10 ml) were added at 0 ЊC
Ϫ
NaBF4 (100 mg, 0.91 mmol) and {[(Me3P)Au]3O}ϩBF4 (110
mg, 0.12 mmol) in dichloromethane (10 ml). The solution was
stirred for 2 h at 0 ЊC and afterwards the solvent removed in
(o-Tol)3PAuOS(O)2CF3 9. To a solution of (o-Tol)3PAuCl
(115 mg, 0.22 mmol) in thf (30 ml) was added at 0 ЊC AgO-
1648
J. Chem. Soc., Dalton Trans., 1999, 1645–1650

View Article Online
Table 1 Crystal data, data collection, and structure refinement for compounds 1, 4, 6 and 9
1
4
6
9ؒCH2Cl2
Formula
Mr
C5H9AuF3O2P
386.06
C5H9AuCl3OPS
451.47
C23H21AuCl3OPS
679.74
C23H23AlCl2F3O3PS
735.31
Crystal system
Space group
Monoclinic
P21/n
Monoclinic
P21/c
Monoclinic
P21/n
Triclinic
P1
¯
a/Å
b/Å
c/Å
α/Њ
9.759(1)
11.362(2)
27.183(3)
6.208(1)
10.216(1)
19.180(2)
11.229(2)
14.256(1)
15.642
10.637(1)
11.303(1)
11.785(1)
67.80(1)
81.99(1)
76.01(1)
1271.1(2)
1.921
β/Њ
99.35(1)
98.70(1)
103.91(1)
γ/Њ
V/Å3
2974.1(7)
2.587
12
1202.4(3)
2.494
4
2430.6(6)
1.858
4
Dc/g cmϪ3
Z
2
F(000)
2112
150.07
Ϫ78
5834
5716 [Rint = 0.0528]
4797
275
832
1312
65.48
Ϫ79
5527
5270 [Rint = 0.0181]
4721
271
712
61.88
Ϫ80
10959
5509 [Rint = 0.0200]
5410
307
µ(Mo-Kα)/cmϪ1
T/ЊC
131.64
Ϫ110
2374
2374
2222
109
Measured reflections
Unique reflections
Reflections for refinement
Refined parameters
Final R values [I > 2σ(I)]
R1
0.0656
0.0507
0.0304
0.0312
wR2
0.1687
3.140/Ϫ3.606
0.1207
2.330/Ϫ2.249
0.0717
1.192/Ϫ2.111
0.0796
1.791/Ϫ2.924
ρfin(max./min.)a/e ÅϪ3
a The residual electron densities were located around Au atoms (compounds 4 and 6) and around the CF3 unit (1), respectively. Absorption correction
by ψ scans was prevented by cooling problems at the end of the measurements.
S(O)2CF3 (55 mg, 0.22 mmol) dissolved in thf (10 ml). After
stirring for 15 min the reaction mixture was filtered. Evapor-
ation of the solvent from the filtrate in vacuo to leave a volume
of ca. 5 ml and addition of pentane led to the precipitation of
136 mg (95%) of complex 9 as a white solid. The compound is
stable in solution only below 0 ЊC, soluble in dichloromethane
and tetrahydrofuran, but insoluble in pentane and diethyl
ether. Colourless crystals suitable for X-ray analysis could be
obtained from dichloromethane solution by layering with pen-
tane at 0 ЊC (Found: C, 37.90; H, 3.24. C22H21AuF3O3PSؒ
CH2Cl2 requires C, 37.57; H, 3.15%). NMR (CDCl3, 0 ЊC): 1H,
δ 6.88–7.74 (m, 12 H, C6H4) and 2.55 (s, 9 H, Me); 13C-{1H},
δ 142.6 [d, J(CP) 13, C2], 133.2 [d, J(CP) 9, C6], 132.0 [d, J(CP)
8, C3], 131.6 [d, J(CP) 3, C4], 126.6 [d, J(CP) 10, C5], 124.6 [d,
J(CP) 60, C1], 121.0 [q, J(CF) 325, CF3] and 22.5 [d, J(CP) 12
Hz, Me]; 31P-{1H}, δ 1.6 (s).
CCDC reference number 186/1388.
See http://www.rsc.org/suppdata/1999/1645/ for crystallo-
graphic files in .cif format.
Acknowledgements
This work was supported by Deutsche Forschungsgemein-
schaft, by Fonds der Chemischen Industrie, by Volkswagen-
stiftung, and, through the donation of chemicals, by Degussa
AG and Heraeus GmbH. The authors are grateful to Mr
J. Riede for establishing the X-ray data sets and Mr S. Gaab for
his experimental support.
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