Auration of the sulfones MeSO2CH2CN and CH 2 (CH2SO2)2CH2

Article abstract of DOI:10.1515/znb-2005-0207

MeSO₂CH₂CN shows considerable C-H acidity at its methylene group. Through lithiation followed by reaction with (Ph ₃P)AuCl it can therefore be readily converted into the dinuclear, geminally substituted product MeSO₂C[Au(PPh₃)] ₂CN. With an excess of aurating reagents, a third [(Ph ₃P)Au] group becomes N-bonded to the nitrile unit to give an ionic trinuclear compound {MeSO₂C[Au(PPh₃)] ₂CNAu(PPh₃)}⁺BF₄^-. The same product is obtained by direct reaction of MeSO₂CH₂CN with [(Ph₃P)Au]BF₄. The crystal structures of the two products have been determined. The diaurated sulfone parts of the molecule and the cation are virtually superimposible. Small Au-C-Au angles and short Au-Au contacts suggest significant aurophilic interactions ("A-frame" structures). The small -C≡N-Au angle of 165.6(5)° in the cation indicates that the strong [(Ph₃P)Au]⁺ acceptor causes substantial changes in the bonding of the nitrile group. Dilithiation of 1,3-dithiane-S,S′-tetroxide followed by reaction with 2 equivalents of (Ph₃P)AuCl affords the geminally diaurated compound CH ₂(CH₂SO₂)₂C[Au(PPh ₃)]₂.

Full text of DOI:10.1515/znb-2005-0207

Auration of the Sulfones MeSO2CH2CN and CH2(CH2SO2)2CH2
Bratislav Djordjevic, Oliver Schuster, and Hubert Schmidbaur
Department Chemie, Technische Universita¨t Mu¨nchen,
Lichtenbergstraße 4, D-85747 Garching, Germany
Reprint requests to Prof. Dr. H. Schmidbaur. E-mail: H.Schmidbaur@lrz.tum.de
Z. Naturforsch. 60b, 169 – 174 (2005); received September 16, 2004
MeSO2CH2CN shows considerable C-H acidity at its methylene group. Through lithiation fol-
lowed by reaction with (Ph3P)AuCl it can therefore be readily converted into the dinuclear, gem-
inally substituted product MeSO2C[Au(PPh3)]2CN. With an excess of aurating reagents, a third
[(Ph3P)Au] group becomes N-bonded to the nitrile unit to give an ionic trinuclear compound
{MeSO2C[Au(PPh3)]2CNAu(PPh3)} BF4−. The same product is obtained by direct reaction of
+
MeSO2CH2CN with [(Ph3P)Au]BF4. The crystal structures of the two products have been deter-
mined. The diaurated sulfone parts of the molecule and the cation are virtually superimposible.
Small Au-C-Au angles and short Au–Au contacts suggest significant aurophilic interactions (“A-
frame” structures). The small -C≡N-Au angle of 165.6(5)◦ in the cation indicates that the strong
[(Ph3P)Au]+ acceptor causes substantial changes in the bonding of the nitrile group. Dilithiation of
1,3-dithiane-S,S’-tetroxide followed by reaction with 2 equivalents of (Ph3P)AuCl affords the gemi-
nally diaurated compound CH2(CH2SO2)2C[Au(PPh3)]2.
Key words: Gold(I) Complexes, Auration, Sulfones, Nitriles, 2,6-Dithiane-S,S’-tetroxide
Introduction
Structural studies of the products have shown that
in the di- or tri-aurated products the Au-C-Au an-
gles are much smaller than expected for a tetrahe-
dral configuration of tetrasubstituted carbon atoms, in
most cases only ca. 90◦ instead of the 109.5◦ stan-
dard. These small angles are associated with short
intramolecular Au–Au contacts in the range from
Auration of organic substrates by strong gold(I)
or gold(III) electrophiles is one of the most attrac-
tive methods of synthesis for organogold compounds
[1 – 3]. The procedure is generally most efficient with
organic compounds exhibiting C-H acidity. Treat-
ment of precursors of t−his type with simple gold(I)
reagents [(L)Au]+ BF4 or with the oxonium salts
{[(L)Au]3O} BF4 leads to an exchange of protons
by the isolobal [(L)Au]+ cations. In most of the cases
documented in the literature, L represents a tertiary
phosphine or arsine. Prominent and classical examples
among the substrates employed are strong C-H acids
like e. g. malodinitrile [4] or 1,3-diketones [5], but also
moderately activated solvents like acetonitrile [6].
˚
2.9 to 3.1 A, very close to the Au-Au distance in
metallic gold and well below the sum of van der
Waals radii, suggesting significant “aurophilic” bond-
ing [9].
As part of a series of studies oriented at an ex-
ploitation of these phenomena for the preparation of
new classes of organogold compounds we have inves-
tigated i. a. the auration of sulfones [5]. With sulfones
physiologically acceptable, gold-substituted sulfones
+
−
Ever since this reaction was discovered, evidence may be of interest in pharmacology. Moreover, polynu-
has accumulated that geminal diauration is a par- clear gold compounds with short gold-gold contacts
ticularly facile process, with the second substitution are known to show intriguing photophysical proper-
often more rapid – and irreversible – than the pre- ties, most notably luminescence, which – owing to the
ceding first step [1, 2]. Even triauration of methyl complexity of the phenomenon – calls for an extended
groups was observed with suitable substrates such as investigation of complexes with a variety of hitherto
methylphosphoniumand –sulf(ox)onium salts or phos- unexplored substituents. The literature has only two
phonium/sulf(ox)oniummethylides [7, 8]. Typically, in reports of previous successful attempts to aurate sul-
these cases one methyl group is fully aurated, while fones [5, 10], in which both mono- and diauration have
others remain untouched.
been documented.
c
0932–0776 / 05 / 0200–0169 $ 06.00 ꢀ 2005 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com

170
B. Djordjevic et al. · Auration of the Sulfones MeSO2CH2CN and CH2(CH2SO2)2CH2
The present report focuses on the behaviour of cy-
anomethyl(methyl)sulfone, CH3SO2CH2CN, in which
the methylene group is activated by both the nitrile
and the sulfone function. For polyauration, the methyl
group potentially offers an alternative site for substi-
tution, which could give access to gold-rich products.
However, the new results show that geminal diauration
at the methylene group and coordination to the nitrile
group are the preferred modes of reaction. A cyclic
disulfone derived from 1,3-dithiane was also included
in the auration studies.
(1)
upon evaporation of the tetrahydrofuran solvent with
dichloromethane gave a 52% yield of the trinuclear
◦
compound (m. p. 186 C).
The same product was obtained in almost quantita-
tive yield by treating MeSO2CH2CN with an equimo-
lar quantity of [(Ph3P)Au]BF4 in tetrahydrofuran at
−78 ◦C (eq. (2, 3)).
Preparative Results
Cyanomethyl(methyl)sulfone was dilithiated at
its methylene group using two equivalents of
nbutyllithium in a tetrahydrofuran/hexane mixed sol-
vent at −78 ◦C and then treated with two equi-
valents of (triphenylphosphine)gold(I) chloride. Af-
ter non-aqueous work-up following standard proce-
dures a colourless crystalline product was obtained in
This result was unexpected, because the 1:1 stoi-
chiometry (in the absence of an auxiliary base) was
chosen for the experiment in order to obtain a 1:1 com-
plex with the [(Ph3P)Au] unit attached to the nitrile
group. Obviously the auration of the methylene group
is faster and irreversible and competes successfully
with the simple C≡N-Au complex formation. With the
chosen 1:1 molar ratio of the reactants, two out of three
sulfone substrates remain unchanged. The results are in
agreement with the course of the auration of the cyano-
◦
82% yield (m. p. 175 C with decomposition). The
dinuclear compound was readily identified by ana-
lytical and spectroscopic data (Experimental Section
and eq. (1)).
methyl(triphenyl)phosphonium cation, which affords
2+
A solution of this diaurated mat◦erial in tetrahydro- the cation {Ph3PC[Au(PPh3)]2C≡N-Au(PPh3)} (as
furan was further treated (at −78 C) with a solution the bis-perchlorate salt) [11].
of an excess of [(Ph3P)Au]BF4, prepared in situ from
The analytical data of the trinuclear product
AgBF4 and (Ph3P)AuCl. Extraction of the residue left confirmed the proposed composition, and the spec-
(2)
(3)
(4)

B. Djordjevic et al. · Auration of the Sulfones MeSO2CH2CN and CH2(CH2SO2)2CH2
171
troscopic characteristics indicated that the third
[(Ph3P)Au] unit [δ 31P 30.0 ppm] was in a differ-
ent environment as compared to the first two [δ 31P
37.1 ppm]. The chemical shift of the latter is in ex-
cellent agreement with that of the dinuclear precursor
1
[δ 31P 37.7 ppm]. Together with the H and 13C NMR
data, this observation suggests that the sulfone part
of the substrate did not undergo major changes in the
last auration step. Surprisingly, however, the nitrile part
also showed only very minor changes in the IR spec-
trum, with ν(C≡N) at 2167 cm−1 (trinuclear) as com-
pared to 2161 cm−1 (dinuclear). The two structures
were finally determined by single crystal X-ray diffrac-
tion studies.
Open-chain 1,3-disulfones have been subjected to
Fig. 1. Molecular structure of MeSO2C[Au(PPh3)]2CN in
its 1:1 acetone solvate (ORTEP, 50% probability ellip-
soids for the core atoms, hydrogen atoms and solvent
auration in a previous study [5]. This investigation
was now extended to the cyclic 1,3-disulfone derived
from 1,3-dithiane. This heterocycle was dilithiated us-
˚
molecule omitted). Selected bond lengths [A] and angles
n
[◦]: C1-C2 1.440(10), C2-N1 1.129(10); C1-S1 1.724(7),
C3-S1 1.809(10), O1-S1 1.431(6), O2-S1 1.458(6); C1-Au1
2.10787), C1-Au2 2.102(6); C2-C1-S1 106,5(5), C2-C1-Au1
111.4(5), C2-C1-Au2 117.0(5), S1-C1-Au1 116.7(4), S1-C1-
Au2 114.6(4), Au1-C1-Au2 90.4(2).
ing two equivalents of butyllithium and subsequently
treated with two equivalents of (Ph3P)AuCl in tetrahy-
◦
drofuran at −78 C to give after standard work-up an
87% yield of the geminally diaurated product. The
same compound was obtained by using methanolic
potassium methoxide as a base with a similar yield
(88%) (eq. (4)). The new diaurated disulfone was iso-
lated as a colourless solid (m.p. 181 ◦C with decompo-
sition), but could not be crystallized. It was identified
by analytical and spectroscopic data.
from the tetrahedral reference. All other angles at C1
are in the range from 106.5(5) to 117.0(5)◦. This dis-
torted tetrahedron is in a staggered conformation rela-
tive to the tetrahedron about the sulfur atom.
The bond lengths show no anomalies, including a
˚
C≡N distance of 1.129(10) A and S=O distances of
Structural Results
˚
1.431(6) and 1.458(6) A. Associated with the small
MeSO2C[Au(PPh3)]2CN
Au1-C1-Au2 angle is a short Au1–Au2 contact of
2.9861(3) A which is indicative of significant au-
rophilic bonding (“A-frame structure”) [9].
˚
Crystals of the dinuclear compound obtained from
acetone solutions as the 1:1 solvate are orthorhombic,
space group P212121, with Z = 4 formula units in the
unit cell (measured at 143 K). The asymmetric unit
contains one independent molecule with no crystallo-
graphically imposed symmetry together with one ace-
tone molecule, which has no unusual intermolecular
contacts. The structure is shown in Fig. 1.
{MeSO2C[Au(PPh3)]2CNAu(PPh3)}+ BF4
−
Crystals of the 1:1 solvate of the trinuclear com-
plex with acetone are monoclinic, space group P21/c,
with Z = 4 formula units in the unit cell. The a−sym-
metric unit contains the complex cation, the BF4 an-
The two gold atoms have become attached to the ion and one acetone molecule (Fig. 2). Between these
carbon atom C1 bridging the sulfone sulfur atom S1 components there are no unusual sub-van der Waals
and the cyano carbon atom C2, replacing the two hy- contacts. The part of the cation which represents the
drogen atoms of the precursor substrate. The coordina- dinuclear precursor molecule is virtually superimposi-
tion geometry at the gold atoms is almost linear, and ble with this substrate. Notable examples are the small
the two phosphorus atoms and the sulfur atom have the Au1-C1-Au2 angle of 89.08(19)◦ and the short Au–Au
˚
standard tetrahedral configuration. Carbon atom C1 is contact of 2.9587(3) A, as well as the staggered con-
also in a quasi-tetrahedral environment, but the geom- formation of the tetrahedra centered by the atoms C1
etry is strongly distorted with an Au1-C1-Au2 angle and S1. As for the dinuclear precursor complex, the
of only 90.4(2)◦, a deviation of almost twenty degrees maximum attainable (mirror) symmetry is not reached

172
B. Djordjevic et al. · Auration of the Sulfones MeSO2CH2CN and CH2(CH2SO2)2CH2
sity at the nitrogen atom. However, surprisingly, this
change is not reflected by the C≡N distances and
by the ν(C≡N) stretching frequencies, which show
only slight differences upon auration, not really reach-
ing out of the standard deviations of the experi-
ments.
Further selected details of the two structures are
given in the figure captions.
Conclusions
The present studies have shown that methyl(cyan-
omethyl)sulfone is readily and selectively aurated by
standard gold(I) electrophiles at the methylene group
to give the geminally dinuclear complex. With ex-
Fig. 2. Structure of the cation in crystals of {MeSO2C
[Au(PPh3)]2CNAu(PPh3)}BF4·Me2CO (ORTEP, 50% prob-
ability ellipsoids for the core atoms, hydrogen atoms, solvent
molecule and c◦ounterion omitted). Selected bond lengths
1.747(5), C3-S1 1.777(6), O1-S1 1.440(4), O2-S1 1.446/4);
Au1-C1 2.125(5), Au2-C1 2.093(5); Au3-N1 2.032(5); C2-
C1-S1 112.2(4), C2-C1-Au1 107.0(4), C2-C1-Au2 118.4(4),
S1-C1-Au1 113.6(3), S1-C1-Au2 114.3(3), Au1-C1-Au2
89.08(19); C2-N1-Au3 165.6(5).
cess reagent, no trinuclear products with hypercoor-
dinate carbon atoms [9, 14, 15] or with an aurated
methyl group are obtained. Terminal complexation at
the nitrile group occurs instead. The reaction path-
ways thus resembles that observed for (cyanometh-
yl)phenylsulfone [5]. The structures of the two prod-
ucts are indicative of significant intramolecular/intra-
ionic aurophilic bonding and a substantial modifica-
tion of the nitrile bonding characteristics upon aura-
tion, which is in agreement with literature data of quite
different classes of compounds [12, 13]. The auration
of the cyclic disulfone followed the pattern already es-
tablished for open-chain sulfones.
˚
[A] and angles [ ]: C1-C2 1.386(7), C2-N1 1.146(7); C1-S1
owing to this conformation, which places one oxygen
atom (O1) between the two gold atoms. This leaves O2
and C3 on the two sides of the potential mirror plane,
instead of the idealized array with O1 and O2 as mirror
images.
The third gold atom is attached to the nitrile ni-
trogen atom, but while the angle C1-C2-N1 remains
linear [178.5(6)◦] the newly formed C≡N-Au angle
(C2-N1-Au3) is much smaller at only 165.6(5)◦. This
result is in agreement with findings for the complex
cation of the related phenylsulfone, which is associ-
ated into a hexanuclear dication: Its C≡N-Au angles
are even smaller at 153.6(5) and 162.6(5)◦ [5]. Because
of the consistent results for different substitution pat-
terns it is unlikely that the deviations of these angles
from the 180◦ standard are due to packing forces in
the crystal, but are an intrinsic structural motif. And
in fact this suggestion is supported by structural data
for [(Ph3P)Au] complexes of quite different substrates
Experimental Section
General: The experiments were carried out in an atmo-
sphere of dry nitrogen. Glassware was oven-dried and filled
with nitrogen, and solvents were distilled, dried and satu-
rated with nitrogen. Standard equipment was used through-
out. CH2(CH2SO2)2CH2 was prepared as described in the
literature [16].
{1,1-Bis[(triphenylphosphine)gold(I)](cyano)methyl}-
(methyl)sulfone
MeSO2CH2CN (24.1 mg, 0.20 mmol) was◦dissolved in
20 ml of tetrahydrofuran and cooled to −78 C. 25 ml of
a 1.6 M solution of nBuLi in hexane was added with stir-
ring, followed after 2 h by a solution of (Ph3P)AuCl (200 mg,
0.40 mmol) in tetrahydrofuran (20 ml). Stirring was contin-
ued over night and over this period the mixture was allowed
to warm to room temperature. The solvents were removed
in a vacuum and the product extracted from the residue with
10 ml of dichloromethane. Evaporation of the solution gave a
colourless microcrystalline precipitate (170 mg, 82% yield).
2+
such as {(tBuNC)2Ru[(Ph2P)2CC≡NAu(PPh3)]2}
or 2-Me-C6H4SO2C(CN)C≡NAu(PPh3) with C≡N-
Au angles of 166.8(13) and 166.3(3)◦, respec-
tively [12, 13].
The data are indicative of a significant change in
the nitrile bonding upon terminal complexation with
a build-up of stereochemically active electron den- Single crystals of a 1:1 solvate could be grown by slow dif-

B. Djordjevic et al. · Auration of the Sulfones MeSO2CH2CN and CH2(CH2SO2)2CH2
173
Table 1. Crystal Data, Data
Collection and Structure Re-
finement Details for MeSO2C-
[Au(PPh3)]2CN · Me2CO and
{MeSO2C[Au(PPh3)]2CNAu-
(PPh3)}BF4 · C3H9O.
MeSO2C[Au(PPh3)]2-
CN · Me2CO
C42H39Au2NO3S
1093.69
orthorhombic
P212121
9.8263(1)
19.0183(2)
20.8216(3)
90
3891.13(8)
1.867
{MeSO2C[Au(PPh3)]2CNAu(PPh3)}-
BF4·Me2CO
C60H54Au3BF4NO3S
1639.72
Empirical formula
M
Crystal system
Space group
monoclinic
P21/c
˚
a [A]
13.6038(1)
23.4226(3)
19.6767(3)
99.8731(15)
6176.86(13)
1.763
˚
a
{Σ[w(Fo2 − Fc2)2] /
b [A]
wR2
=
˚
Σ[w(Fo2)2]}1/2; w = 1/[σ2(Fo2) +
(ap)2 +bp]; p = (F2 + 2F2)/3.
c [A]
β [◦]
o
c
3
˚
V [A ]
ρcalc [g cm−3
]
Z
4
4
F(000)
2104
77.07
143
3136
72.73
143
µ (Mo-Kα ) [cm−1
T [K]
]
Refls. Measured
Refls. Unique
84668
7123 [Rint = 0.079]
463 / 0
0.0273
0.0572
135423
10933 [Rint = 0.065]
640 / 0
0.0338
0.0675
Refined param. /restraints
R1[I ≥ 2σ(I)]
wR2a
Absolute structure factor
Weighting scheme
0.005(7)
a = 0.0084
b = 11.4973
0.890 / −0.617
a = 0.0147
b = 23.7971
1.067 / −0.857
−3
]
˚
σ
fin(max/min) [eA
fusion of pentane vapour into a solution of the compound in (58 mg, 0.30 mmol) and (Ph3P)AuCl (150 mg, 0.30 mmol)
◦
acetone at −10 ◦C.
in 10 ml of the same solvent at −78 C with stirring. The
reaction mixture was stirred over night while it warmed up
to room temperature. Evaporation of the solvent and extrac-
tion of the residue afforded a solution of the product, which
was recovered upon evaporation of the dichloromethane sol-
vent as a colourless solid (m.p. 186 ◦C with decomposition)
in an almost quantitative yield (158 mg, 98%). Single crys-
tals could be grown by slow diffusion of pentane vapour into
a solution of the compound in acetone at −10 ◦C.
◦
NMR (CD2Cl2, 20 C), 1H: δ = 7.11 – 7.85 (m, 30 H,
Ph); 3.20 (s, 3 H, Me); 13C{ H}: δ = 134.6 (d, J = 14 Hz,
1
C2/6), 131.9 (s, C4), 128.6 (d, J = 54.5 Hz, C1), 129.2
(d, J = 11 Hz, C3/5), 46.9 (s, Me), CN and CAu2 not de-
1
tected; 31P{ H}: δ = 37.7 (s). MS (FAB): m/z 1492 (7%)
[M + AuL]+; 1034 (39) [M]+; 720 (72) [L2Au]+; 458
(100) [LAu]+ (L = Ph3P). IR (KBr): 2161.5 cm−1, ν(C≡N).
C30H33Au2NO2P2S·Me2CO (1093.68): calcd. C 46.12,
H 3.59; found C 45.74, H 3.41.
NMR (CD2Cl2, 25 ◦C), 1H: δ = 7.23 – 8.15 (m,
45 H, Ph); 3.23 (s, 3 H, Me); 13C{ H}: δ = 129.4 –
1
135.1 (Ph), 48.5 (s, Me), CN and CAu2 not detected;
{1,1-Bis[(triphenylphosphine)gold(I)](N-[(triphenylphos-
phine)gold(I)]cyano)methyl}-(methyl)sulfon tetrafluoro-
borate
31P{ H}: 37.1 (s, 2 P), 30.0 (s, 1 P). MS (FAB): m/z
1
1494 (3%) [M-BF4]−, 720 (88) [L2Au]+, 459 (100)
[LAu]+, 262 (4) [L]+. IR (KBr): 2167 cm-1, ν(C≡N).
C57H48Au3BF4NO2P3S·Me2CO (1639.72), calcd. C 43.95,
H 3.32; found C 42.86, H 3.13.
Method 1: A solution of [(Ph3P)Au]BF4 was prepared
by reacting AgBF4 (56 mg, 0.29 mmol) and (Ph3P)AuCl
(143 mg, 0.29 mmol) in tetrahydrofuran (10 ml) at
◦
−78 C with stirring for 2 h. Subsequently a solution of
1,1-Bis[(triphenylphosphine)gold(I)]-2,6-dithiane-S,S’-
tetroxide
MeSO2C[Au(PPh3)]2CN (150 mg, 0.14 mmol) in 10 ml of
tetrahydrofuran was added and the reaction mixture stirred
over night while it was allowed to warm to room tempera-
ture. The solvents were evaporated and the residue extracted
with dichloromethane (10 ml). The solvent was again evap-
orated and the residue washed with pentane to leave 119 mg
(52% yield) of a colourless microcrystalline product.
Method 1: A solution of 1,3-dithiane-S,S’-tetroxide
(37 mg, 0.20 mmol) [16] in 10 ml of tetrahydrofuran was
lithiated◦with 0.25 ml of a 1.6 M solution of nBuLi in hexane
at −78 C for 2 h. Subsequently a solution of (Ph3P)AuCl
(200 mg◦, 0.40 mmol) in 10 ml of tetrahydrofuran was added
Method 2: MeSO2CH2CN (36 mg, 0.30 mmol), dissolved at −78 C and the reaction mixture stirred for 3 h while
in 10 ml of tetrahydrofuran, was added to a solution of it was allowed to warm up to room temperature. After
[(Ph3P)Au]BF4 in tetrahydrofuran, prepared from AgBF4 evaporation of the solvent the residue was extracted with

174
B. Djordjevic et al. · Auration of the Sulfones MeSO2CH2CN and CH2(CH2SO2)2CH2
dichloromethane and the product isolated as a colourless employing graphite-monochromated Mo-Kα radiation. In-
solid by evaporation of the solvent from the extract (185 mg, tensity data were corrected for absorption effects (DELABS
87% yield, m. p. 181 ◦C with decomposition).
from PLATON). The structures were solved by a combina-
tion of direct methods (SHELXS-97) and difference-Fourier
syntheses and refined by full matrix least-squares calcula-
tions on F2 (SHELXL-97) [17]. The thermal motion of all
non-hydrogen atoms was treated anisotropically. All hydro-
gen atoms were calculated and allowed to ride on their parent
atoms with fixed isotropic contributions.
Further information on crystal data, data collection and
structure refinement are summarized in Table 1. Anisotropic
displacement parameters and tables of interatomic distances
and angles have been deposited with the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK. The data are available on request on quoting
CCDS-250555 & 250556.
Method 2: The same quantities of the disulfone and the
gold(I) complex (above) were dissolved in a solution of KOH
(23 mg, 0.40 mmol) in 10 ml of methanol and the reac-
tion mixture stirred for 3 h at room temperature. Removal of
the methanol in a vacuum and extraction of the residue with
dichloromethane gave 193 mg of the product (88% yield).
◦
NMR (CD2Cl2, 20 C), 1H: δ = 7.15 – 7.90 (m, 30 H,
Ph), 3.17 (m, 4 H, CCH2), 2.42 (m, 2 H, CH2); 13C{ H}:
1
δ = 134.6 (d, J = 14.0 Hz, C2/6), 132.1 (s, C4), 131.5 (d, J =
54.5 Hz, C1), 129.6 (d, J = 11.9 Hz, C3/5), 52.3 (s, SCH2),
1
38.7 (s, CH2); 31P{ H}: δ = 38.7 (s). MS (FAB) m/z =
1100 (9.8%) [M]+; 721 (50.6) [L2Au]+; 459 (100) [LAu]+.
C40H36Au2O4P2S2 (1100.72), calcd. C 44.71, H 3.30; found
C 44.71, H 3.42.
Acknowledgements
Crystal structure determination
This work was generously supported by Deutsche
Specimens of suitable quality and size were mounted on Forschungsgemeinschaft, by Fonds der Chemischen Indus-
the ends of quartz fibers in F06206R oil and used for inten- trie, and – through the donation of chemicals – by Heraeus
GmbH.
sity data collection on a Nonius DIP 2020 diffractometer,
[7] H. Schmidbaur, F. Scherbaum, B. Huber, G. Mu¨ller,
Angew. Chem. Int. Ed. Engl. 27, 419 (1988).
[8] J. Vicente, M. T. Chicote, R. Guerrero, P. G. Jones,
J. Am. Chem. Soc. 118, 699 (1996).
[9] H. Schmidbaur, Chem. Soc. Rev. 24, 391 (1995).
[10] H.-J. Kneuper, K. Harms, G. Boche, J. Organomet.
Chem. 364, 275 (1989).
[1] H. Schmidbaur, Organogold Compounds, Gmelin
Handbook of Inorganic Chemistry, Springer, Berlin
(1980).
[2] H. Schmidbaur, A. Grohmann, M. E. Olmos, A. Schier,
in S. Patai, Z. Rapoport (eds): The Chemistry of Or-
ganic Derivatives of Gold and Silver, p. 227, Wiley,
New York (1999).
[11] J. Vicente, M.-T. Chicote, M.-C. Lagunas, Helv. Chim.
Acta 82, 1202 (1999).
[12] M. E. G. Mosquera, J. Ruiz, V. Riera, Organometallics
20, 3821 (2001).
[3] A. Grohmann, H. Schmidbaur, in E. W. Abel,
F. G. A. Stone, G. Wilkionson (eds): Comprehen-
sive Organometallic Chemistry, Vol. 2, p. 1, Pergamon,
Oxford (1994).
[13] E. Fritsch, K. Polborn, K. Su¨nkel, W. Beck, Z. Anorg.
Allg. Chem. 617, 110 (1992).
[4] E. I. Smyslova, E. G. Perevalova, V. P. Dyadchenko,
K. I. Grandberg, D. A. Lemenovski, T. V. Baukova,
O. B. Afanossova, J. Organomet. Chem. 65, 131 (1974).
[5] B. Djordjevic, K. A. Porter, S. Nogai, A. Schier,
H. Schmidbaur, Organometallics 22, 5336 (2003) and
ref. therein.
[6] a) E. G. Perevalova, T. V. Baukova, V. P. Dyadchenko,
E. I. Smyslova, Y. L. Slovokhotov, K. I. Grandberg,
Bull. Acad. Sci. USSR, Chem. Ser. 2529 (1983); b) K. I.
Grandberg, V. P. Dyadchenko, J. Organomet. Chem.
474, 1 (1994) (Review); J. Vicente, M. T. Chicote, Co-
ord. Chem. Rev. 193 – 195, 1143 (1999) (Review).
[14] a) N. Dufour, A. Schier, H. Schmidbaur,
Organometallics 12, 2408 (1993); b) S. Bom-
mers, H. Beruda, N. Dufour, M. Paul, A. Schier,
H. Schmidbaur, Chem. Ber. 128, 137 (1995).
[15] H. Schmidbaur, F. P. Gabba¨ı, A. Schier, J. Riede,
Organometallics 14, 4969 (1995).
[16] J. R. Meadow, E. E. Reid, J. Am. Chem. Soc. 56, 2177
(1934).
[17] G. M. Sheldrick, SHELX-97, Programs for Crystal
Structure Analysis, University of Go¨ttingen, Germany
(1997).