Gold clustering at Dimethylsulfoximine Me2S(O)NH

Article abstract of DOI:10.1515/znb-2000-1001

Polyaurated complexes of the dimethylsulfoximide anion [Me₂S(O)N]^- have been prepared by reacting N-trimethylsilyl-dimethylsulfoximide with [(Ph₃P)Au]BF₄ in various molar ratios. With one or two equivalents of t

Full text of DOI:10.1515/znb-2000-1001

Gold Clustering at Dimethylsulfoximine Me2S(0)NH
Armin Hamel, Christian Hollatz, Annette Schier, and Hubert Schmidbaur
Anorganisch-chemisches Institut, Technische Universität München,
D-85747 Garching, Germany
Reprint requests to Prof. H. Schmidbaur. E-mail: H.Schmidbaur@lrz.tum.de
Dedicated to Prof. Dr. Dr. h. c. Max Schmidt on the occasion ofhis 75th birthday
Z. Naturforsch. 55 b, 889-894 (2000); received August 8, 2000
Gold Clustering, Dimethylsulfoximine
Polyaurated complexes of the dimethylsulfoximide anion [Me2S(0 )N]_ have been prepared
by reacting N-trimethylsilyl-dimethylsulfoximide with [(Ph3P)Au]BF4 in various molar ratios.
With one or two equivalents of the gold(I) reagent only the dinuclear complex is obtained in
high yield: {[(Ph3P)Au]2NS(0 )Me2}+BF4-. With three or four equivalents only the trinu-
clear complex is produced: {[(Ph3P)Au]3NS(0 )Me2}2+2 BF4-. No mono- or tetra-auration
was observed, respectively. The composition of the compounds has been confirmed by ana-
lytical and spectroscopic data, and the crystal structure of the dinuclear compound has been
determined by single crystal X-ray diffraction of the dichloromethane solvate. The two gold
atoms are found to be coordinated to the nitrogen atom with a small Au-N-Au angle of only
92.3(3)° and a short Au-Au distance of 2.9900(5) A. The nitrogen atom is in a distorted
trigonal pyramidal configuration which allows an intramolecular SO-Au contact. For the tri-
nuclear complex a structure with a tetracoordinate nitrogen atom [SNAU3] is proposed which
is analogous to the corresponding complexes of phosphinimines R3P=NH. With the ditertiary
phosphine Ph2PCH2Ch2PPh2 (dppe) a cyclic dinuclear complex (dppe)Au2[NS(0 )Me2]BF4
can be synthesized starting from (dppe)Au2Cl2. The reaction of the phosphine-rich precursor
[(Ph3P)2Au]BF4 with Me3SiNS(0 )Me2 in the molar ratio 2:1 affords a binuclear complex
{[(Ph3P)2Au]2NS(0 )Me2}BF4 of an as yet unknown structure.
Introduction
phinimines R3P=NH [13]. Up to three [LAu]+units
could be assembled at the nitrogen atom of such
phosphinimines to give dications [R3PN(AuL)3 ]2+.
In the present study the clustering of [LAu]+
moieties at the nitrogen atom of a sulfoximine
R2 S(0 )=NH has been investigated in order to probe
the influence of a neighbouring oxo centre on the
donor capabilities of the imines.
The organometallic chemistry of dialkylsulfox-
imines was studied in this laboratory in the past
[14], but gold was not considered as a partner ele-
ment in this earlier program.
Owing to their unique electron characteristics
[1-3] complex gold(I) units [LAu]+(L = donor
ligand) show many unexpected bonding phenom-
ena. One of the most striking observations made
in recent years in many laboratories has been
the clustering of such units around boron, car-
bon, nitrogen / phosphorus / arsenic, and oxygen
/ sulfur / selenium donor centres [4], Homoleptic
substitution to give polycations like [(LAu)nC]m+,
[(LAu)nN/P/As]m+ or [(LAu)nO/S/Se]m+ is com-
plemented by clustering at partially substituted
heteroatoms as in species like [RC(AuL)n]m+,
[RN(AuL)n]m+or [RO(AuL)n]m+or their phospho-
rus and sulfur/selenium analogues [5].
Preparative, Analytical and Spectroscopic Results
Dimethylsulfoximine is readily prepared from
dimethylsulfoxide an hydrazoic acid, the latter be-
Clustering at nitrogen [6 ] is particularly com-
mon and was found to occur readily at ammonia ing generated in situ from sodium azide and an acid
[7], hydrazine [8 ], hydroxylamine [9], primary and
secondary amines and amides [1 0 ], and a variety
of imines [11]. This chemistry not only includes
standard aldimines and ketimines (Schiff bases
RR'C=NH), but also carbodiimines [12] and phos-
in chloroform. The product can be converted into
the N-trimethylsilyl derivative by treatment with
trimethylchlorosilane in the presence of a base (tri-
ethylamine) in toluene (eq. (1))- N-Trimethylsilyl-
dimethylsulfoximide is a distillable liquid, which
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890
A. Hamel et al. ■Gold Clustering at Dimethylsulfoximine Me2S(0 )NH
is a very convenient reagent in sulfoximine chem-
istry [14]. It was alsousedexclusively in thepresent which show the v(S=0) vibration to be largely un-
is also supported by the IR data (for Nujol mulls),
study.
changed as compared to the starting material. The
crystal structure of the compound has been deter-
mined and the results verify the structural model
with both gold atoms coordinated to the nitrogen
centre also for the solid state (below).
Me2SO +NaN3
■Me2S(0)NH
(1)
Me2S(0)NH +Me3SiCl ^
^
1
1Me2S(0)NSiMe3
The most common and most powerful aurat-
ing agents for the introduction of [LAu]+ units
with
From experiments with the reagents in the molar
ratio 1:3 in dichloromethane (at -20 °C) a differ-
ent product was obtained in high yield (83%, m. p.
115 °C with decomposition), which is also colour-
less and has similar solubility properties (eq. (3)).
L = PPh3 are (triphenylphosphine)gold
tetrafluoroborate [which cannot be isolated and
is prepared in situ from (triphenylphosphine)gold
chloride [15] and silver tetrafluoroborate], or
{tris[(triphenylphosphine)gold]oxonium} tetraflu- Me2S(0)NSiMe3+3 [(Ph3P)Au]BF4
oroborate (which can be isolated and stored) [16].
(3)
NaBF4 >{Me2S(0)N[AuPPh3]3}[BF4]2
Both reagents were used successfully in the
present investigation, but the preparations with
[(Ph3P)Au]BF4 were more convenient.
The analytical data (Exp. Part) indicate that the
expected rr/nuclear compound has been formed.
Again only a singlet 31P resonance is observed
(29.6 ppm) which suggests that all three Ph3P lig-
ands areequivalent. The 1H resonance ofthe methyl
groups is shifted to 3.72 ppm, while the phenyl
multiplet is largely unchanged as compared to the
dinuclear product. The 13C{1H} spectrum has asin-
gle set of phenyl resonances proving that all 9 aryl
groups are equivalent. The mass spectrum (FAB)
does not show the complete trinuclear d/cation, but
features [(Ph3P)2 Au]+and [(Ph3 P)Au]+asthe main
fragments.
Treatment of Me2 S(0 )=NSiMe3 with
[(Ph3P)Au]BF4 in the molar ratio of 1:1 in
dichloromethaneatroomtemperaturegaveacolour-
less product in less than 50% yield, which was
shown to be thed/nuclear (below) instead of the ex-
pected mononuclear complex. It therefore appears
that the d/auration of the sulfoximine is at least
faster or even thermodynamically more favoured
than complete mwioauration. From reactions with
the 1 : 1 stoichiometry of reagents one half of the
sulfoximine is recovered unchanged.
The crystals of the rr/nuclear compound did not
have the quality to allow the determination of the
solid state structure by X-ray diffraction. It should
be noted, however, that crystal structures ofthecor-
responding triorganophosphinimines (A) have been
determined. The three gold atoms arealways bound
to one common nitrogen atom ofthed/cations [13].
Based on this analogy, a structure (B) is proposed
for the trinuclear sulfoximide complex which has a
tetrahedrally four-coordinated nitrogen atom.
Attempts to aurate the sulfoximine further by ap-
plying an even greater molar ratio of reactants (1:4)
under similar conditions gave only the rr/nuclear
For the 1:2 stoichiometry of reagents very high
yields (89%) ofthe^/nuclearcomplex wereisolated
(eq. (2)). The product is a robust, colourless, crys-
talline solid (m. p. 122 °C with decomposition).
Me2S(0)NSiMe3+2 [(Ph3P)Au]BF4
NaBF^ >{Me2S(0)N[AuPPh3]2}BF4
(2)
The product is stable in moist air as a solid and
in solution (di- and trichloromethane, tetrahydro-
furan). It is readily identified by its analytical and
spectroscopic data. The mass spectrum shows the
parent cation (m/z 1010) in high abundance. The
31 P{1H} NMR spectrum has a singlet resonance at
6
32.0 ppm (CDCI3 ), and the ’H NMR spectrum a
singlet at 3.42 for the methyl and a multiplet for
thephenyl protons(7.35 -7.65). Theaniongivesrise
to a nB resonance at -1.25 ppm. The NMR data
O
12©
6
? I 2®
R -P—R
Me—S—Me
6
Auf^Au
A u4 > u
indicate that the two phosphine ligands and the two
methyl groups are equivalent, ruling out a structure
with one [LAu]+at nitrogen and theotherat oxygen
(or carbon) for the solution state. This conclusion
Ph3P
Au XPPh3
Ph3P
‘Au XPPh3
PPh3
(A)
PPh3
(B)
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A. Hamei et al. ■Gold Clustering at Dimethylsulfoximine Me2S(Q)NH
891
compound. The excess of the gold fluoroborate
(dppe)(AuCI)2 -----
-—*- (dppe)(AuBF4)2
was found to decompose upon work-up causing
low yields and poorer quality of the product. It
should be noted that the quadruply aurated species
{Me2S(0 )N[Au(PPh3 )]4}3+would bear a very high
positive charge (3+) which is likely to destabilise
the system even if the oxo centre is employed as
an auxiliary donor. Homoleptic pentacoordination
of nitrogen by gold atoms is however well estab-
lished [6 ].
Monoauration of the nitrogen function in
dimethylsulfoximine with [(Ph3P)Au]+ units
proved impossible. The diauration appears to be
kinetically or - more likely - thermodynamically
more favoured (above). The open coordination
sphere at two-coordinate gold(I) leads to signifi-
cant Au-Au interactions which induce polyaura-
tion. At sterically more crowded gold centres (with
Me2S(0)NSiMe3
/—
\
~i®
(5)
Ph2P^
PPh2
Au^ ^Au
N
BF4"
Me2S=0
tions in CDCI3 show a 31P resonance at 27.6 ppm,
a 11B resonance at -1.19 ppm and 1H resonances at
3.74 (s, Me), 2.78 (A2 A'2XX') and 7.25 -7.55 (Ph).
The mass spectrum shows the ion [(dppe)Au]+. A
cyclic structure is proposed for this compound, but
there is no proof as yet from X-ray diffraction anal-
ysis.
two phosphine ligands) this tendency should be re- The Structural Chemistry of
duced. Therefore Me2S(0 )=NSiMe3 was also re-
acted with [(Ph3P)2 Au]+BF4 _ [17] in the molar ra-
tio 1:1inthepresenceofNaBF4 inCH2 CI2 (Eq. (4)).
{Me2S(0)N[Au(PPh3)]2}+BF4-
Crystals of the dinuclear compound (from
dichloromethane / pentane) are monoclinic, space
group P2]/n, with Z = 4 molecular units and four
molecules of dichloromethane in the unit cell.
The lattice contains cations, anions and solvent
molecules well separated with no significant sub-
van-der-Waalscontacts. Thecationhasnocrystallo-
graphically imposed symmetry and the coordinates
of the atoms deviate strongly from the maximum
possible symmetry operation, a mirror plane pass-
ing through N, S and O and bisecting the Au-N-Au
angle.
2 [(Ph3P)2Au]BF4+Me2S(0)NSiMe3
— {[(PPh3)2Au]2NS(0)Me2}BF4
(4)
According to microanalytical data the product ob-
tained did not have the composition of a mononu-
clear complex, but appeared to be the correspond-
ing dinuclear complex. This compound was indeed
formed in high yield from the analogous reaction
with the reagents in the molar ratio 1:2 (85% yield,
m. p. 112 °C with decomposition). The product has
a singlet 31P (27.6 ppm) and a singlet nB reso-
nance (-1.19 ppm), a singlet 'H signal at 3.74 ppm
Both gold atoms are coordinated to the nitrogen
(Me) and a multiplet at 7.25 -7.55 ppm (Ph). The atom with an angle Aul-N-Au2 of only 92.3(3)°.
mass spectrum shows the ions [(Ph3 P)2 Au]+and This small angle is associated with a short au-
[(Ph3 P)Au]+. The structure of this compound is un- rophilic contact Aul-Au2 of2.9900(5) A. The con-
known. No single crystalscould be grown for X-ray figuration at the gold atoms is close to linear (N-
diffraction analysis.
Aul-P2 175.4(2), N-Au2-Pl 173.1(2)°]. Most sig-
The preference for d/auration is also confirmed nificantly, the configuration at the nitrogen atom
by the course of the reaction of Me2 S(0 )=NSiMe3 is not planar. The sum of the angles Aul/2-N-S
with the dinuclear gold complex of the diter- 114.5(5)/121.5(5)° andAul-N-Au292.3(3)° isonly
tiary phosphine PhbPCF^CFbPPt^ (dppe). A bis- 328.3° indicating a large deviation from planarity.
tetrafluoroborate was first prepared in situ from
(dppe)(AuCl)2 [18] and two equivalents of AgBF4
The sulfoxide unit 0 =SMe2 isclearly tiltedtowards
one of the gold atoms (Aul) (Fig. 1). This struc-
in CH2CI2 at -20 °C and then treated with the N- tural detail is at variance with the characteristics
trimethylsilylsulfoximide in the presence of NaBF4 of the analogous dinuclear phosphinimine cation,
(Eq. 5).
A colourless crystalline product was obtained in
{Ph3P-N[Au(PPh3 )]2 }+where the imine nitrogen
atom has been found to be in aplanar configuration
81% yield (mp. 109°C with decomposition). Solu- and the R3P group in a symmetrical position [13].
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892
A. Hamei et al. ■Gold Clustering at Dimethylsulfoximine Me2S(0 )NH
gold(I) [18] were prepared following literature methods.
NaBF4and AgBF4 were commercially available.
N,N-Bis[(triphenylphosphine)gold(I)Jdimethyl-
sulfoximide(+) tetrafluoroborate(-)
From Ph3AuCl (0.297 g, 0.60 mmol) and AgBF4
(0.117 g, 0.6 mmol) in 10 ml of CH2C12 a solution of
[(Ph3P)Au]BF4 is prepared and treated with a solution
ofMe3SiNS(0)Me2(0.049 g, 0.3 mmol) in the same vol-
ume of the same solvent. After addition ofasmall amount
of solid NaBF4 the reaction mixture is stirred for 2 h at
r. t. The solution turns pink. It is filtered and the volume
of the filtrate is reduced to 3 ml in a vacuum. Addi-
tion of diethylether (30 ml) gives a colourless precipitate
Fig. 1. Molecular structure of the cation of
{Me2S(0)N[Au(PPh3)]2}BF4 x CH2C12. (ORTEPdraw-
ing with 50% probability ellipsojds, H atoms omitted for
clarity). Selected bond lengths [A] and angles [°]: Aul-N
2.087(8), Au 1-P22.233(2), Aul -Au2 2.9900(5), Au2-N
2.061(8), Au2-Pl 2.234(2), N-S 1.522(8), S-0 1.453(8),
S-Cl 1.754(10), S-C2 1.748(10); N-Aul-P2 175.4(2), N-
Au2-Pl 173.1(2), S-N-Au2 121.5(5), S-N-Aul 114.5(5),
Au2-N-Aul 92.3(3).
of the product, which is filtered and recrystallized from
CH2C12/ pentane (0.293 g, 89% yield, m. p. 122 °C with
decomp.). NMR, ’H:
6 3.42 (s, 6H, Me), 7.35 -7.65 (m,
30H, Ph);11B: -1.25 (s);31P{1H}: 32.0 (s). MS(FAB): m/z
1010 [M-BF4]+, 459 [(Ph3P)Au]+.C38H36Au2BF4NOP2S
(1097.47) calcd. C 41.59, H 3.31, N 1.28; found C 41.49,
H 3.66, N 1.04.
The same dinuclear product is obtained from
Me3SiNS(0)Me2 (0,049 g), (Ph3P)AuCl (0.148 g) and
AgBF4 (0.059 g, 0.3 mmol each) in 20 ml of CH2C12
(0.07 g yield; same analytical and spectroscopic data).
The differences probably arise from a weak inter-
action of the oxo function S=0 with one of the
two gold atoms (Aul). Both the pyramidalization
of the N(S,Au,Au) unit and the tilt of the Me2 SO
unit bring the two atoms (Aul, O) closer together
[Aul-O 3.485 A].
N,N,N-Tris[(triphenylphosphine)gold(I)]dimethyl-
sulfoximide(2+) bis[tetrafluoroborate(-)]
Conclusions
A solution of the silylsulfoximide (0.049 g, 0.3 mmol)
in 20 ml of CH2C12 is treated (at -20 °C) with a solu-
tion of [(Ph3P)Au]BF4 prepared from 0.9 mmol each of
(Ph3P)AuCl (0.445 g) and AgBF4 (0.175 g) in 30 ml of
the same solvent containing some NaBF4. After 30 min
the mixture is allowed to warm to room temperature and
is stirred for 2 h. The mixture is filtered, the filtrate con-
centrated to a volume of 5 ml and layered with petroleum
ether. A fine colourless precipitate is obtained (0.41 g,
83% yield, m.p. 115 °C with decomp.). NMR, 'H: 3.74
(s, 6H, Me), 7.25-7.55 (m, 45 H, Ph); "B: -1.31 (s);
13C{]H}: 77.1 (s, Me), 126.5 (d, Cip,0, J = 66 Hz), 129.7
The imine function in asulfoximine isreadily au-
rated with the usual aurating agents [LAu]+X- to
give di- and trinuclear complexes. The gold atoms
are coordinated to the nitrogen atoms with small
angles Au-N-Au which favour aurophilic bonding
(Au-Au). In theexample forwhich adetailed struc-
ture analysis is available, the sulfoxide group is ori-
entedtowards oneofthegold atoms and maintains a
significant Au-O contact. The nitrogen atomattains
apyramidal configuration and the tilt of the sulfox-
ide group reduces the symmetry ofthecationic unit.
(d, Cmeta, 7=13 Hz), 132.8 (d, Cpara,
J = 3 Hz), 133.9 (d,
Cortho, 7=14 Hz);31P{1H}: 29.6 (s). MS(FAB): m/z 720
[(Ph3P)2Au]+, 459 [(Ph3P)Au]+. C56H5iAu3B2F8NOP3S
(1643.53) calcd. C 40.83, H 3.34, N 0.85; found C 40.02,
H 3.2, N 0.8.
Experimental Part
All experiments were routinely carried out in an
atmosphere of pure and dry nitrogen. Solvents and
glassware were dried and saturated / filled with nitro-
gen. Standard equipment was used throughout. N-Tri-
methylsilyl-dimethylsulfoximide [14], (triphenylgold(I)
chloride [15], bis(triphenylphosphine)gold(I) chloride
[17], and [l,2-bis(diphenylphosphino)ethane]dichlorodi-
The same trinuclear product is obtained from the
reagents in
a 1:4 ratio: Me3SiNS(0)Me2 (0.049 g,
0.3 mmol), (Ph3P)AuCl (0.594 g), AgBF4 (0.236 g,
1.2 mmol each); 20 + 40 ml of CH2C12, -20 °C, 0.5
+ 2 h (0.39 g yield; same analytical and spectroscopic
data).
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A. Hamei et al. ■Gold Clustering at Dimethylsulfoximine Me2S(0 )NH
893
Bis[bis(triphenylphosphine)gold(l)Jdimethyl-
sulfoximide(+) tetrafluoroborate(-)
(971.29): calcd. C 34.62, H 3.11, N 1.44; found C 34.13,
H 3.21, N 1.50.
A
solution of [(Ph3P)2Au]BF4 is prepared from
Crystal structure analysis
(Ph3P)2AuCl (0.378 g) and AgBF4 (0.097 g, 0.5 mmol
each) in 40 ml of CH2CI2 at -20 °C and filtered into a so-
lution ofMe3SiNS(0)Me2(0.041 g, 0.25 mmol) in 10 ml
of the same solvent containing some NaBF4.The mixture
is allowed to warm up to room temperature and is then
stirred for another 2 h. After filtration the volume of the
filtrate is reduced to 5 ml and petroleum ether is added
to precipitate the colourless product (0.657 g, 84% yield,
m. p. 112 °C with decomp.). NMR, 'H: 3.06 (s, 6H, Me),
7.37 -7.73 (m, 60 H, Ph); "B: -1.27 (s); 3IP{'H}: 30.8
(s). MS(FAB): m/z 720 [(Ph3P)2Au]+, 459 [(Ph3P)Au]+.
C74H66Au2BF4NOP4S (1622.08): calcd. C 54.79, H 4.10,
N 0.86; found C 54.21, H 4.14, N 0.81.
The data were collected on a Nonius KappaCCD
area detector equipped with a rotating anode (Nonius
FR591). Graphite-monochromated Mo-KQradiation was
used. The structure was solved by a combination of direct
methods and difference-Fourier syntheses and refined by
full matrix least-squares calculations on F2. The thermal
motion was treated anisotropically for all non-hydrogen
atoms. Hydrogen atoms were calculated and allowed to
ride on their corresponding C atoms with fixed isotropic
contributions.
Crystal data for
C39
H
38AU
2
BCI
2
F
4
NOP
2S: Mx =
1182.35, colorless crystals, monoclinic,
a
= 9.881(1),/? =
24.490(1), c= 17.468(1) Ä, ß= 102.234(1)°, space group
P2,/n, Z = 4, V= 4131.06(11) A3, pcMc = 1-901 gem“3,
F(000) = 2264; T = 0 °C. 70534 measured and 8426
unique reflections [R\nl = 0.0865]; 478 refined parame-
The same dinuclear product is obtained from the
reagents in a 1:1 molar ratio: Me3SiNS(0)Me2(0.082 g),
(Ph3P)2AuCl (0.378 g), AgBF4(0.097 g, 0.5 mmol each),
20 +40 ml of CH2C12, -20 °C, 0.5 + 2 h (0.34 g yield,
same analytical and spectroscopic data).
ters, wR2 = 0.1264,
R = 0.0554 for 8426 reflections used
for refinement. Residual electron densities: +2.40/-2.14
e/A3(located around the gold atoms). The function mini-
mized was: wR2 = {[Zw(F02 -Fc2)2]/X[w(F02)2]}1/2;w=
[l,2-Bis(diphenylphosphino)ethane]digold(I)-p-N,N-
dimethylsulfoximide(+) tetrafluoroborate(-)
1/[ct2(F02) +(ap)2+bp]-,p =
(F02+2Fc2)/3; a = 0.0264,
b
= 67.93. Important interatomic distances and angles
A solution of [bis(diphenylphosphino)ethane]digold(I)
bis(tetrafluoroborate), (dppe)Au2(BF4)2,is prepared from
(dppe)Au2Cl2 (0.036 g, 0.041 mmol) and AgBF4
(0.0156 g, 0,082 mmol) in 20 ml of CH2C12 at -20 °C
and filtered into a solution of Me3SiNS(0)Me2(0.0067 g,
0.041 mmol) in 10ml ofthe same solvent containing some
NaBF4. After 30 min the reaction mixture is allowed to
warm to room temperature and stirred for 2 h. After fil-
tration the filtrate is concentrated to a volume of 3 ml and
layered with petroleum ether to give a white microcrys-
talline precipitate (0.03 g, 80.6% yield, m. p. 109 °C with
decomp.) NM R,1H: 2.78 (m, 4H, CH2), 3.74 (s, 6H, Me),
7.25 -7.55 (m, 20 H, Ph); UB: -1.19 (s); 3iP{'H}: 27.6
(s). MS(FAB): 595 [(dppe)Au]+. C28H30Au2BF4NOP2S
are given in the figure caption. Anisotropic thermal pa-
rameters and complete lists of interatomic distances and
angles have been deposited with the Cambridge Crystal-
lographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK. The data are available on request on quoting
CCDC-148154.
Acknowledgement
This work was supported by Deutsche Forschungsge-
meinschaft, Fonds der Chemischen Industrie, and Volks-
wagenstiftung. Donations of chemicals by Degussa-Hüls
AG and Heraeus GmbH aregratefully acknowledged. The
authors thank Ms. M. Grosche for establishing the X-ray
data set.
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A. Hamel et al. ■Gold Clustering at Dimethylsulfoximine Me2S(0)NH
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