Thiolate complexes of gold(I) based on a tris(phosphine) support

Article abstract of DOI:10.1515/znb-2001-1202

Treatment of the ligand 1,3,5-tris[(diphenylphosphanyl)methyl]trimethylbenzene (P₃) with (tetrahydrothiophene)gold(I) chloride results in the symmetrical trigold complex [(P₃)(AuCl)₃]. In the presence of sodium methoxide, [(P₃)(AuCl)₃] reacts with thiocresol (HSC₆H₄Me-4) and 2-mercaptoquinoline (2-HSQn) to provide the complexes [(P₃)(AuSC₆H₄Me-4)3] and [(P₃)(AuSQn)₃], respectively, Reaction of [(P₃)(AuCl)₃] with KSCN also yields the expected product [(P₃)(AuSCN)₃], however, treatment with 2 - 10 molar equivalents of NaSMe results only in the unsymmetrical cationic complex [(P₃)Au₃(SMe)₂]Cl. Reaction between [(P₃)(AuOTf)₃] (prepared in situ from [(P₃)(AuCl)₃] and AgOTf) and sodium sulfide yields the complex [(P₃)Au₃S]⁺OSO₂CF₃ ^-, the first example of a trigoldsulfonium unit coordinated to a tridentate phosphine. The tetrafluoroborate salt is obtained from [(P₃)(AuCl)₃] and Na₂S · 9 H₂O in the presence of NaBF₄. The structure of [(P₃)(AuSMe)2]Cl has been determined and reveals that in the solid the two methylthiolate units bridge the three gold atoms, but the structure of the cation is fluxional in solution according to NMR data.

Full text of DOI:10.1515/znb-2001-1202

Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
James D. E. T. Wilton-Ely, Stefan Hofreiter, Norbert W. Mitzel, and Hubert Schmidbaur
Anorganisch-chemisches Institut der Technischen Universität München,
Lichtenbergstrasse 4, D-85747 Garching, Germany
Reprint requests to Prof. Dr. H. Schmidbaur. E-mail: H.Schmidbaur@lrz.tum.de
Z. Naturforsch. 56 b, 1257-1263 (2001); received September 11, 2001
Gold(I) Complexes, Tri(tertiary phosphine) Complexes, Thiolate Complexes
Treatment of the ligand l,3,5-tris[(diphenylphosphanyl)methyl]trimethylbenzene (P3) with
(tetrahydrothiophene)gold(I) chloride results in the symmetrical trigold complex [(P3)(AuC1)3].
In the presence of sodium methoxide, [(P3)(AuC1)3] reacts with thiocresol (HSCöH4Me-4)
and 2-mercaptoquinoline (2-HSQn) to provide the complexes [(P3)(AuSC6H4Me-4)3] and
[(P3)(AuSQn)3], respectively. Reaction of [(P3)(AuCl)3] with KSCN also yields the expected
product [(P3)(AuSCN)3], however, treatment with 2 - 1 0 molar equivalents of NaSMe re-
sults only in the unsymmetrical cationic complex [(P3)Au3(SMe)2]Cl. Reaction between
[(P3)(AuOTf)3] (prepared in situ from [(P3)(AuC1)3] and AgOTf) and sodium sulfide yields
the complex [(P3)Au3S]+0 S02CF3_, the first example of a trigoldsulfonium unit coordinated
to a tridentate phosphine. The tetrafluoroborate salt is obtained from [(P3)(AuCl)3] and Na2S
• 9 H2Oin the presence of NaBF4. The structure of [(P3)(AuSMe)2]Cl has been determined
and reveals that in the solid the two methylthiolate units bridge the three gold atoms, but the
structure of the cation is fiuxional in solution according to NMR data.
Introduction
phino)ethyl)]amine ligand (NP3) was found to react
with [LAuCl] (L = tetrahydrothiophene, PPh3) to
give the cations [Au(NP3)]+X_ (X = Cl- , PFö- ,
NO3- , Scheme 1, a) for which X-ray structures
(of the PFö“ and NO3- salts) were established [9].
It was discovered that if BPh4~ was employed
as a counteranion, a quite different structure was
adopted in which each of two NP3 ligands binds
in a bidentate manner at one gold atom while the
third phosphine ‘arm’ reaches across to bind to the
second gold center (Scheme 1, b). The complexes
ClAuP[(CH2)wPPh2AuCl]2 (n = 1 [10 ], n = 2 [1 1 ])
shown in Scheme 1, c have also been prepared and
used in the synthesis of thiolate complexes [12 ].
Both complexes display gold-gold contacts between
the three gold atoms. The trication ‘sandwich’ com-
plex [{Ph2PCH2P(Ph)CH2PPh2}2Au3](SCN)3 [13]
(Scheme 1, d) has been prepared directly from
KAuCU and the ligand in the presence of NaSCN
and bis(2-hydroxyethyl)sulfide. The structure of the
complex displays particularly short aurophilic inter-
actions in the range 2.95 - 2.96 A.
Gold metal has a remarkable affinity for the heav-
ier chalcogen elements and a large number of com-
pounds with sulfur donors have been reported [1].
Thiolate complexes make up the most common class
of gold(I) compounds with sulfur and many applica-
tions (medicine [2], self-assembly monolayers [3],
liquid golds for ceramics [4]) have been found for
this class of compounds. Some early observations in
sulfur chemistry were followed by the preparation
of the synthetically highly versatile oxonium salts
[0 (AuPPh3)3]+ in 1980 [5], which are analogues of
the corresponding complexes of the heavier chalco-
gen elements [A(AuPPh3)3]+ (A = S, Se, Te [6 , 7]).
These thrice aurated complexes are among the best-
known examples of multiply-aurated main group
elements (C, N, P, S, Se, Te). In many cases, the syn-
thesis can be broken down into individual auration
steps involving the successive addition of [AuPR.3]+
units. These results have shown that auration of
sulfide goes well beyond the 2:1 stoichiometry of
Au2S [8].
A
recent report from these laboratories
The coordination of gold(I) centers to triden- concerned the preparation of the complex
tate tertiary phosphine ligands has been the subject
of a number of reports. The tris[2-(diphenylphos-
[Ph(ClAu)P{C6H4P(AuCl)Ph2-2 }2] (Scheme 1, e)
from the tridentate phosphine [PhP(C6H4PPh2-2)2].
0932-0776/01/1200-1257 $ 06.00 (c) 2001 Verlag der Zeitschrift für Naturforschung, Tübingen • www.znaturforsch.com
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J. D. E. T. Wilton-Ely et al. •Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
Ph
13®
Ph2
All
Ph,
Cl
ju
Cl
Cl
T
Au
1
1
©
Ph2P'
-PPh,
Ph2Pv
Ph2P ^ / ^ ^ P P h 2
\ ; u
p
/
lk
/
PPhi
Ph
Ph
Ph,
c
AuCI
AuCI
fj>Ph2
Ph2l
Scheme 1. A se-
lection of reported
[tris(phosphine)]-
gold(I) compounds,
and complex h =
[(P3)(AuC1)3] (1).
1
f U
|u
Cl
Cl
Cl
A variable temperature NMR study performed on desired trigold complex [(P3)(AuCl)3] (1 ) in excel-
this system proved that the aurophilic contacts lent yield (Scheme 2). A singlet was observed in
found in the solid state persist in solution [14] and
that the bond energy was also in good agreement symmetrical geometry for the complex in solution.
the 31P NMR spectrum at 29.9 ppm indicating a
with that calculated previously [15].
Singlet (1.78 ppm) and doublet (3.84 ppm, Jpu =
13.0 Hz) resonances were observed in the *H NMR
spectrum for the methyl and methylene protons, re-
spectively. The singlets at 135.8 (C2,4’6Q M e3) and
131.0 (C1,3,5C6Me3) ppm in the 13C NMR spectrum
are in accordance with the presence of only two car-
bon environments for the central aromatic ring. In
the same spectrum, peaks were observed for the
methylene carbon atoms at 31.8 (d, Jpc = 23.0 Hz)
ppm whereas the singlet observed at 20.3 ppm was
assigned to the methyl carbons. Additional char-
acteristic resonances were present for the aromatic
carbon atoms of the other phosphine substituents.
Microanalytical data showed that the complex crys-
tallizes as a dichloromethane trisolvate.
The first sulfur donor to be investigated as a ligand
for the complex was thiocyanate which reacted to
yield the expected compound [(P3)(AuSCN)3] (2).
A 3:2 ratio was observed in the !H NMR spectrum
for the methyl and methylene protons and analytical
data confirmed the overall molecular composition.
The 31P NMR spectrum displayed a broad singlet
suggesting that the three phosphine ‘arms’ are not
rigidly fixed at room temperature. The same ob-
servation was made for all subsequent trithiolate
species.
The structure of the tri[chlorogold(I)] com-
plex of the tris(diphenylphosphino)methane (tppm)
ligand [(tppm)(AuCl)3] (Scheme 1, f) was
found to contain aurophilic contacts of 3.20 A
[16], however, the related bis(tppm) complex
[Au2(tppm)(AuCl)](C104)2 (Scheme 1 , g) displays
even shorter distances between gold atoms (2.92 -
3.09 A) due to a constrained geometry [17].
Recent research in these laboratories has cen-
tered on tailoring ligands to provide a favorable
coordination geometry for the attached gold cen-
ters [14, 16, 18]. Such a ligand was provided by
the synthesis of the species 1,4-bis(diphenylphos-
phanylmethyl)benzene which provided the requi-
site 90° angle for the coordination of an [AUS2]
unit [18]. This led us to prepare a tris(phosphine)
variant with an even greater degree of flexibility in
the phosphine ‘arms’. We present here the results
of an investigation into the coordination chemistry
of this ligand, l,3,5-tris[(diphenylphosphanyl)me-
thyl]trimethylbenzene (P3), with gold(I) (Scheme 1,
h), and the subsequent reactivity with sulfur donors.
Synthesis and Characterization of Complexes
The tris(phosphine) ligand l,3,5-tris[(diphe-
The coordinating abilities of two other thiolates
nylphosphanylmethyl)trimethylbenzene] (P3 ) was (p-thiocresol, 2 -mercaptoquinoline) were also ex-
found to react cleanly with three molar equivalents amined. These reactions were performed in the pres-
of either (tht)AuCl or (Me2S)AuCl to provide the ence of sodium methoxide in order to aid deproto-
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J. D. E. T. Wilton-Ely et al. •Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
1259
Scheme 2. Preparation of the
complexes, (i) 3[(Me?S)AuCl];
(ii) 3KSCN; (iii) 3HSTol
(Tol = C6H4Me-4), 3NaOMe;
(iv) 3HSQn (Qn = quinoline),
3NaOMe; (v) 2 - 1 0 mol. eq.
NaSMe (vi) 3AgOTf, Na2S.
did not provide the expected 2:3 ratio of methyl-
ene to S-methyl protons expected for a product
of composition [(P3)(AuSMe)3], but instead re-
vealed a 1:1 ratio. This indicated formation of
a product containing only two methylthiolate lig-
ands. There is precedence for the coordination of
more than one gold center to a single sulfur donor
(see introduction) and a structural investigation re-
vealed that this had indeed occurred. The iden-
tity of the product (Scheme 3) was confirmed as
the compound [(P3)Au3(SMe)2lCl (5) in which the
three gold centers are bridged by only two SMe
groups (see structural section). If viewed care-
fully, it becomes apparent that there are similar-
ities between this arrangement and that found in
the complexes [(MeC6H4S2-3 ,4 )(AuPPh3)3]+ and
[(CH2S)2(AuPPh3)3]+ in which the AuPPh3 units
each bridge two sulfur atoms [19, 20]. What was
more unexpected was the fact that the same prod-
uct was obtained on reaction of [(P3)(AuCl)3] (1 )
with two, three or even ten molar equivalents of
sodium methylthiolate. The related bis(phosphine)
variants [CöH4(CH2PPh2AuSMe)2-l,4 ] and [C6H4-
(l,4 -CH2PPh2Au)2SMe]BF4 have been prepared
from [C6H4(CH2Ph2PAuCl)2-l,4 ], however, the
Me
Me
I©
S
A
, / 1
Au-Au
Au
\
PPh,
/
PPh2
Ph?P
Scheme 3. Schematic drawing of the cation in com-
pound 5.
nation of the thiol and led to the complexes [(P3)-
(AuSC6H4Me-2)3] (3) and [(P3)(AuSQn)3] (SQn =
quinoline thiolate) (4), respectively. The spectro-
scopic data associated with the tris(phosphine) lig-
and are found to be almost identical to that ob-
tained for the previous complexes. In the 1H NMR
spectrum, compound 3 showed a number of new
resonances attributed to the aromatic protons (6.89,
7.08 ppm, AB system, 7hh =8.1 Hz) and methyl pro-
tons (2.43 ppm) of the tolylthiolate group. In con-
trast, however, the peaks due to the quinolinethiolate
ligand for complex 4 were not as clearly resolved
and were observed as a series of multiplets.
Treatment of complex 1 with three molar equiv-
alents of NaSMe yielded a pale yellow product.
The 31P NMR spectrum displayed a single broad- formation of the different products was deter-
ened peak at 36.4 ppm. However, the integra- mined through varying the stoichiometry of the
tion of the !H NMR spectrum for this species reagents [12]. This suggests perhaps that the greater
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J. D. E. T. Wilton-Ely et al. ■Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
flexibility of the P3 ligand compared to the related
1 ,4-substituted bis(phosphine) species plays a role
in the structure of 5. A comparison of 5 with the
other two thiolate complexes [(P3)(AuSR)3] [R =
CöH4Me-4 (3), quinoline (4)] would suggest that a
cationic, bridged, dithiolate species is favored for
the compact methylthiolate ligand over the conven-
tional trithiolate structure proposed for the com-
plexes 3 and 4. The reasons for this are not entirely
clear but the comparatively electron-rich nature of
the methylthiolate ligand could provide a clue as to
why only two ligands are required for the stability
of 5 whereas three thiolate ligands (bearing electron
withdrawing tolyl or quinoline substituents) are re-
quired for complexes 3 and 4. It is less likely but
still possible that steric factors also have a role to
play.
Fig. 1. Molecular structure of the cation in crystals of 5
x CH2CI2 x 1.5 H20.
Having succeeded in bringing two gold centers
together through a sulfur donor, it was clear that
the next challenge would be the preparation of a
[(R3PAu)3S]+ analogue. Two synthetic routes were
employed. The first involved the treatment of com-
plex 1 with three equivalents of AgOSC>2CF3 to
provide an in situ solution of [(P3)(AuOTf)3] and
subsequent addition of an excess of sodium sul-
fide. The second was the more direct addition of an
aqueous solution of Na2S • 9 H2O and NaBF4 to 1.
Both were found to yield the desired salts with the
cation [(P3)Au3S]+ (6 ) in which all three gold cen-
ters are bound to the same sulfur atom. In contrast
to the other thiolate complexes discussed above, the
31P NMR spectra for 6 displayed a sharp peak at
37.8 ppm indicating a restriction on movement of
the phosphine ‘arms’, in accordance with the pro-
posed structure. The ]H NMR provided a 3:2 ratio
for S-methyl and methylene proton resonances at
1.76 (s) and 4.08 (d, 7PH = 11.9 Hz) ppm. Of all
the compounds presented here, only the cations 5
and 6 provided useful FAB mass spectrometric data.
The molecular ion observed in the FAB mass spec-
trum of complex 6 at m/z = 1338 supports the pro-
posed composition, as do the microanalytical data.
This is the first time that all three gold atoms of
a trigold(trisphosphine) complex have been coordi-
nated to a single sulfur atom.
plex (no exclusion of air humidity), are triclinic,
space group P I, with Z= 2 formula units in the unit
cell, together with two CH2CI2 solvent molecules
and three molecules of water, one of which is dis-
ordered. The anions and cations are well separated
with no conspicuous sub-van-der Waals contacts.
The structure of the cation is shown in Fig. 1.
The three gold atoms are all positioned on one side
of the trifunctional arene ligand. Each phosphorus
atom bears one gold atom, and two methylthio-
late groups are in bridging position between these
gold atoms. Thus SI is connecting Au2 and Au3,
while S2 is connecting Aul and Au3. Au3 is there-
fore three-coordinate, while Aul and Au2 are two-
coordinate. The angle Aul-S2-Au3 is very small
[81.7(1)°] which brings the two gold atoms rather
close together [Aul--Au3 3.1357(9) A] suggest-
ing aurophilic bonding. The angle Au2-Sl-Au3
[98.1(1)°] is larger which leads to a much longer
contact Au2- -Au3 = 3.645(1) A, already at the limit
of significant metal-metal interactions.
Both sulfur atoms are in a pyramidal configura-
tion with sums of their three angles at 316.6 (SI)
and 290.6° (S2), respectively. The methyl group at
S1 is oriented towards the center of the complex, but
that at S2 is pointing towards the periphery avoiding
a steric conflict.
If the unsymmetrical structure of the cation is
retained in solution, it would require three inequiv-
alent phosphorus atoms to be detected in the NMR
spectrum, and the three methyl groups of the central
Structural Discussion
Crystals of compound 5, grown by diffusion of
pentane into a dichloromethane solution of the com-
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J. D. E. T. Wilton-Ely et al. ■Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
1261
using deuterated solvents with the usual standards at
25 °C. The species HSC6H4Me-4, KSCN, NaSMe, 4-
mercaptoquinoline, sodium sulfide and AgOTf were ob-
tained commercially. The phosphine ligand, 1,3,5-tris-
[(diphenylphosphanylmethyl)trimethylbenzene] (P3) was
prepared following the procedure reported by Aguiar and
Daigle [21]. The species [ClAu(tht)] (tht = tetrahydroth-
iophene) [22] and [ClAu(SMe2)] [23] were synthesized
according to the literature methods.
[(PsXAuClh] (1)
A
solution of P3 (1.43 g, 2.00 mmol) in
dichloromethane (100 ml) was added dropwise to a
stirred solution of [ClAu(SMe2)] (1.77 g, 6.00 mmol)
in dichloromethane (50 ml). After stirring for 2 h, the
solvent volume was reduced to ca. 20 ml and pentane
(60 ml) added to precipitate the colorless product. Yield:
95% (2.86 g). 31P{‘H} NMR (CDCI3): 29.9 (s) ppm.
'H NMR (CDCI3): 1.78 (s, 9 H, CH3), 3.84 (d, 6 H,
C(33>
Fig. 2. Atomic numbering of all non-hydrogen atoms in
the cation of 5.
arene ring should also be inequivalent, as should be
the two methylthiolate groups etc. The room tem-
perature spectra of compound 5 show equivalence
of these atoms and groups, however, suggesting a
fluxional behaviour rendering the atoms equivalent
on the NMR time-scale. Low temperature spectra
(to -60°C) did not give the expected full resolu-
tion, probably because some of the intramolecular
motions are still not sufficiently slow under these
conditions.
CH2,
/
p h
=
13.0 Hz), 7.43
-
7.67 (m, 30 H, C6H5)
ppm. I3C{'H} NMR (CDCI3): 135.8 (m, C2’4’6C6Me3),
133.6 (d, o/m-C6H5, Jcp = 13.0 Hz), 132.2 (s, p-C6U5),
131.0 (m, C ''3’5C6Me3), 129.6 (d, ipso-C(,U5, Jcp =
61.0 Hz), 128.4 (d, o/m-CtH5, J c p = 13.0 Hz), 31.8 (d,
CH2, J c p = 23.0 Hz), 20.3 (s, CH3) ppm. Analysis for
C48H45AU3CI3P3 • 3 CH2C12: calcd. C 36.75, H 3.08;
found C 36.33, H 3.13. The dichloromethane tris-solvate
was confirmed by integration of the 1H NMR spectrum.
[(p3)(AuScN)3] (2)
There is precedence for this type of fluxionality,
even for closely related cases with two thiolate lig-
ands bridging three gold atoms. Compound 5 is the
only case, however, where the terdentate ligand has
potential threefold symmetry.
A methanolic solution (10 ml) of KSCN (21 mg,
0.071 mmol) was added to
a stirred solution
of [(P3)(AuC1)3] (1) (100 mg, 0.071 mmol) in
dichloromethane (25 ml). After stirring for 1h, the solu-
tion was filtered through diatomaceous earth to remove
precipitated KC1. Ethanol (10 ml) was added and the sol-
vent volume reduced to precipitate the colorless product
in 57% (60 mg) yield. The product is slightly soluble in
ethanol, however this provides better quality crystals than
precipitation with pentane. 31P{1H} NMR (CDCI3): 36.9
(s) ppm. 'H NMR (CD2CI2): 1.82 (s, 9 H, CH3), 3.98
(d, 6 H, CH2, / p h = 12.1 Hz), 7.51 - 7.75 (m x 2, 30
H, C6H5) ppm. Analysis for C51H45AU3N3P3S3 •CH2CI2:
calcd. C 39.91, H 3.01, N 2.69; found C 39.68, H 3.01, N
2.31. The monodichloromethane solvate was confirmed
by integration of the 1H NMR spectrum.
Conclusion
As a result of both pharmacological applica-
tion and academic interest, (phosphine)gold(I) thi-
olate chemistry has been widely investigated. The
use of tris(phosphines), however, has been less
well explored and this work demonstrates how a
tris(phosphine) base can be designed in order to
serve as a platform for the mutual interaction of
several gold centers. This provides an indication
of the way in which patterns of even more com-
plex aggregates based on polydentate donors can be
achieved.
[(P3)(AuSC6H4Me-4)3] (3)
Experimental Section
[(P3)(AuCl)3] (1) (100 mg, 0.071 mmol) and
HSCöH4Me-4 (30 mg, 0.242 mmol) were dissolved in
dichloromethane (20 ml) and a methanolic solution (5 ml)
General Information. The experiments were carried
out routinely in air. NMR: JEOL GX 400 spectrometer
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J. D. E. T. Wilton-Ely et al. •Thiolate Complexes of Gold(I) Based on a Tris(phosphine) Support
solvent volume was reduced to ca. 5 ml and pentane
(20 ml) added to precipitate the colorless product in 78%
(61 mg) yield. b)[(P3)(AuCl)3](l)( 100 mg, 0.071 mmol)
was dissolved in dichloromethane (20 ml) and an aque-
ous (15 ml) mixture of Na2S •9 H20 (50 mg, 0.21 mmol)
and NaBF4 (30 mg, 0.27 mmol) was added. The bipha-
sic mixture was stirred for 3 h. The non-aqueous layer
was decanted and the aqueous layer washed twice with
of NaOMe (1 3 mg, 0 .2 4 1 mmol) added. After stirring for
1 h, the solution was filtered through diatomaceous earth
to remove precipitated NaCl. Diethyl ether (2 5 ml) was
added to precipitate the colorless product in 70% (8 3 mg)
yield. 31P{!H} NMR (CDClj): 3 5 .0 (s) ppm. 'H NMR
(CDC13): 1 .7 6 (s, 9 H, CH3), 2 .4 3 (s, 9 H, tolyl-CH3),
3 .7 4 (d, 6 H, CH2, 7 ph = 1 0 .6 Hz), 6 .8 9 ,7 .0 8 (AB system,
12 H, C6H4, 7 hh
= 8.1 Hz), 7 .4 6 , 7 .6 8 (m, 3 0 H, C6H5)
ppm. Analysis for C69H66AU3P3S3: calcd. C 4 9 .4 7 , H dichloromethane (10 ml). The extracts were combined
3 .9 7 ; found C 4 9 .2 0 , H 3 .9 6 .
and the solvent volume reduced to ca. 5 ml and diethyl
ether (20 ml) added to precipitate the colorless prod-
uct in 62% (63 mg) yield. MS (FAB) m/z = 1338, 66%
[M]+. 31P{‘H} NMR (CD2C12): 37.8 (s) ppm.'H NMR
(CD2C12): 1.76 (s, 9 H, CCH3), 4.08 (d, 6 H, CH2, / PH=
11.9 Hz), 7.51 - 7.95 (m, 30 H, C6H5) ppm. Analysis for
C49H45Au3F30 3P3S2; calcd. C 39.57, H 3.03; found C
39.68, H 3.30.
[(P3)(AuSQn)3] (4)
A methanolic solution (10 ml) of HSQn (34 mg,
0.211 mmol) and NaOMe (13 mg, 0.241 mmol) was
added to a stirred solution of [(P3)(AuCl)3] (1) (100 mg,
0.071 mmol) in dichloromethane (25 ml). After stir-
ring for 1 h, the solution was filtered through diatoma-
ceous earth to remove precipitated NaCl. Pentane (25 ml)
was added to precipitate the colorless product in 64%
(81 mg) yield. 31P{’H} NMR (CDC13): 34.5 ppm. ]H
NMR (CDCI3): 1.80 (s, 9 H, CH3), 3.68 (d, 6 H, CH2,
7 ph = 7.4 Hz), 7.26 - 7.82 (m, 51 H, C6H5 + SQn) ppm.
Analysis for C78H66AU3P3S3 • 2 CH2C12: calcd. C 49.19,
H 3.61; found C 48.56, H 3.86.
X-ray crystallography
A specimen of suitable quality and size of compound 5
was mounted on the end of a quartz fiber in F06206R
oil and used for intensity data collection on a Non-
ius DIP2020 diffractometer, employing graphite-mono-
chromated Mo-K^ radiation. The structure was solved by
a combination of direct methods (SHELXS-97) and dif-
ference-Fourier syntheses and refined by full matrix least-
squares calculations on F 2 (SHELXL-97). The thermal
motion was treated anisotropically for all non-hydrogen
atoms. All hydrogen atoms were calculated and allowed
to ride on their parent atoms with fixed isotropic contri-
butions.
Crystal datafor C5/H56Au3Cl3Oi.sP3S2: M = 1547.24,
triclinic, a = 9.4468(3), b = 13.8460(5), c = 19.9789(9) Ä,
a = 86.057(1), ß = 88.580(2), 7 = 84.255(4)°, space
group P \ , Z = 2 , V = 2593.5(2) A3, T = 148 K, *t(Mo-
KQ) = 88.29 cm-1, 99208 measured and 9877 unique
reflections (R\nt = 0.620), wR2 = 0.1437, R\ = 0.0604 for
9877 reflections [I > 2a (/)] and 582 parameters.
Thermal 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 quot-
ing CCDS-170631.
[(p3)Au3(SMe)2]Cl (5)
An aqueous solution (5 ml) of NaSMe (10 mg,
0.143 mmol) was added to
a stirred solution of
[(P3)(AuCl)3] (1) (100 mg, 0.071 mmol) in acetone
(30 ml). After stirring for 1 h, all solvent was removed.
The crude product was redissolved in dichloromethane
(20 ml) and filtered through diatomaceous earth to re-
move precipitated NaCl. Pentane (20 ml) was added to
precipitate the colorless product in 63% (62 mg) yield.
MS (FAB) m/z = 1399, 100% [M]+. 31P{'H} NMR
(CD2C12): 34.6 [s(br)] ppm.'H NMR (CD2C12): 1.76 (s,
9 H, CCH3), 2.53 (s, 6 H, SCH3) 4.01 (d, 6 H, CH2, / PH=
12.1 Hz), 7.48 - 7.85 (m, 30 H, C6H5) ppm. Analysis
for C50H5,AU3CIP3S2: calcd. C 41.83, H 3.56; found C
41.31, H 3.80.
[(p3)Au3S]BF4/OTf (6)
a)
[(P3)(AuCl)3] (1) (74 mg, 0.05 mmol) and
Acknowledgements
A g0S02CF3 (41 mg, 0.16 mmol) were stirred in tetrahy-
drofuran (30 ml) for 10 min at 0°C. This solution was fil-
tered through diatomaceous earth into a tetrahydrofuran
(10 ml) solution of Na2S • 9 H20 (25 mg, 0.10 mmol).
After stirring for 2 h, all solvent was removed and the
crude product redissolved in dichloromethane (20 ml)
and again filtered through diatomaceous earth. The
Support of this work by the Deutsche Forschungsge-
meinschaft, the Volkswagenstiftung, the Alexander von
Humboldt Stiftung (J. D. E. T. W.-E.), and the Fonds der
Chemischen Industrie is gratefully acknowledged. The
authors are also indebted to Degussa AG and Heraeus
GmbH for the donation of chemicals.
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1263
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