Gold(I) complexes with the ligand 1-thiolate-1,2-dicarba-closo-dodecaborate. Crystal structure of [Au2(1-S-1,2-C2B10H11) 2(μ-dppe)]

Article abstract of DOI:10.1016/S0022-328X(98)00500-2

Neutral and anionic gold(I) mononuclear derivatives with the 1-thiolate-1,2-dicarba-closo-dodecaborate ligand of stoichiometries [Au(1-S-1,2-C₂B₁₀H₁₁)L] and [Au(1-S-1,2-C₂B₁₀H₁₁)₂]^- have been synthesised. The complex [Au(1-S-1,2-C₂B₁₀H₁₁)(AsPh₃)] is a good starting material for the synthesis of the dinuclear gold(I) derivative [Au₂(1-S-1,2-C₂B₁₀H₁₁) ₂(μ-PP)], where PP is a diphosphine. The compound [Au₂(1-S-1,2-C₂B₁₀H₁₁)(PPh ₃)₂]BF₄ has also been prepared. The structure of the neutral complex [Au₂(1-S-1,2-C₂B₁₀H₁₁) ₂(μ-dppe)] is confirmed by single-crystal X-ray diffraction. There are no short gold-gold interactions.

Full text of DOI:10.1016/S0022-328X(98)00500-2

Journal of Organometallic Chemistry 561 (1998) 1–6
Gold(I) complexes with the ligand
1-thiolate-1,2-dicarba-closo-dodecaborate. Crystal structure of
[Au2(1-S-1,2-C2B10H11)2(v-dppe)]
M. Mar Artigas a, Olga Crespo a, M. Concepcio´n Gimeno a, Peter G. Jones b,
Antonio Laguna a,*, M. Dolores Villacampa a
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSlC, 50009 Zaragoza, Spain
b Institut fu¨r Anorganische und Analytische Chemie der Technischen Uni6ersita¨t, Postfach 3329, D-38023 Braunschweig, Germany
Received 12 May 1997; received in revised form 11 February 1998
Abstract
Neutral and anionic gold(I) mononuclear derivatives with the 1-thiolate-1,2-dicarba-closo-dodecaborate ligand of stoi-
chiometries [Au(1-S-1,2-C2B10H11)L] and [Au(1-S-1,2-C2B10H11)2]− have been synthesised. The complex [Au(1-S-1,2-
C2B10H11)(AsPh3)] is a good starting material for the synthesis of the dinuclear gold(I) derivative [Au2(1-S-1,2-C2B10H11)2(v-PP)],
where PP is a diphosphine. The compound [Au2(1-S-1,2-C2B10H11)(PPh3)2]BF4 has also been prepared. The structure of the
neutral complex [Au2(1-S-1,2-C2B10H11)2(v-dppe)] is confirmed by single-crystal X-ray diffraction. There are no short gold–gold
interactions. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Gold(I); o-Carborane; Thiolate
1. Introduction
the following fields: synthesis of polymers [6], homoge-
nous catalysis [7], boron neutron capture therapy [8].
As a continuation of our investigations of the synthe-
sis and reactivity of gold and silver derivatives with
carborane ligands [9], our attention is now centred on
the chemistry arising from monosubstituted ligands
based on o-carborane. Their preparation is not an easy
task because of the great tendency of the monolithiated
carborane derivative to disproportionate. Recently,
Hawthorne et al. prepared monosubstituted compounds
[10] by blocking one position using the bulky group
SiMet2Bu to form the monolithiated derivative. Teixidor
et al. [11] prevented dilithiation by using dimethoxy-
ethane as solvent and prepared [1-(PPh2)-1,2-C2B10H11]
and [1-(SH)-1,2-C2B10H11], but no chemistry of these
ligands has been reported to the best of our knowledge.
Here we present the first results in the study of the
reactivity of the monothiolate [1-(SH)-1,2-C2B10H11]
ligand.
Thiolate compounds enjoy increasing interest because
of their varied chemistry; worthwhile topics for study
include the potential of complexes with respect to SꢀC
bond cleavage reactions and desulphurisation [1], the
novel structures of some coordination complexes [2]
and the possibility of stabilisation of unusual oxidation
states. Applications in the study of biological systems
[3] and use in medicine as antiarthritric or cancerostatic
drugs [4] also contribute to the growing interest in these
compounds. Our recent work has focused on the prepa-
ration of thiolate gold complexes with carborane lig-
ands [5] because of their potential applications, the
result of the specific properties of carborane clusters, in
* Corresponding author. Tel.: +34 76 761185; fax: +34 76
567920; e-mail: alaguna@posta.unizar.es
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00500-2

2
M.M. Artigas et al. / Journal of Organometallic Chemistry 561 (1998) 1–6
Scheme 1.
In the positive ion mass spectra (FAB+) of these
2. Results and discussion
derivatives the most intense peaks are assigned to the
fragments [AuL]+ and [AuL2]+. The molecular peak
[M]+ is only present in the spectrum of complexes 2
and 4 [m/z=572 (5%) (2), 679 (17%) (4)]. However, the
peak assigned to [M+AuL]+ [1094 (8%) (1), 970
(10%) (2), 1157 (7%) (3), 1181 (17%) (4)] is always
observed, which implies a considerable stability for
such dinuclear complexes. Thus, we attempted the reac-
tion of 1-(SH)-1,2-C2B10H11 with [O{Au(PPh3)}3]BF4.
This reaction affords the dinuclear cationic complex
[Au2(1-S-1,2-C2B10H11)(PPh3)2]BF4 (5) (see Scheme 1).
In the IR spectrum of 5, the absorption correspond-
ing to the BꢀH stretching band of the carborane moiety
is observed at 2585 cm−1. The absorptions wd(BF) and
The reaction of 1-thiol-1,2-dicarba-closo-dodecabo-
rane with [AuClL] in dichloromethane and in the pres-
ence of Na2CO3 affords the thiolate gold(I) complexes
[Au(1-S-1,2-C2B10H11)L] [L=PPh3 (1), PPh2Me (2),
SPPh3 (3), AsPh3 (4)] (see Scheme 1). Complexes 1–4
behave as non-conductors in acetone solutions and are
moisture- and air-stable. Their IR spectra show a broad
absorption centred between 2572 and 2602 cm−1 (vs,
br) arising from the BꢀH stretching modes of the
o-carborane nucleus [12].
1
In the H-NMR spectra of these complexes, a signal
for the CH proton is observed at about 3.8 ppm (Dl on
comparing different complexes is B0.3 ppm); the sig-
nal from the phenylic protons in complexes 1–4 and
the doublet from the methylene protons in compound 2
are also present.
wd(FBF) of the anion BF4 are at 1068 and 537 cm−1
,
respectively [13].
The 31P{1H}-NMR spectrum presents a singlet for
the two equivalent phosphorus atoms at 35.6 ppm (s),
shifted downfield from compound 1.
The 31P{1H}-NMR spectra of complexes 1–3 show a
singlet for the phosphorus atom shifted downfield from
the starting materials.
Complex 5 exhibits the cation/ion molecular peak in
the positive ion fast atom spectrum at m/z=1094

M.M. Artigas et al. / Journal of Organometallic Chemistry 561 (1998) 1–6
3
Fig. 1. Molecule of complex 6 in the crystal with the atom numbering scheme. Displacement parameter ellipsoids represent 50% probability
surfaces. H atoms are omitted for clarity.
The structure of complex 6 has been established by
X-ray diffraction and is shown in Fig. 1, with selected
bond lengths and angles in Table 1, and atomic coordi-
nates in Table 2. The molecule possesses crystallo-
graphic inversion symmetry. The gold atoms display an
essentially linear geometry, with PꢀAuꢀS 176.06(3)°.
The gold centres are bridged by one diphosphine ligand
(20%), although the most intense peak is assigned to
[Au(PPh3)]+ (m/z=459).
The complex [Au(1-S-1,2-C2B10H1)(AsPh3)] (4) reacts
with diphosphines in the molar ratio 2:1 to afford the
dinuclear compounds [Au2(1-S-1,2-C2B10H1)2(v-PP)]
[PP:
dppe=1,2-bis(diphenylphosphino)ethane
(6),
dppp=1,3-bis(diphenylphosphino)propane (7)] which
are moisture- and air-stable.
˚
with AuꢀP distances of 2.2621(9) A, similar to those
observed in complexes containing the analogous dithio-
late: [Au2(v-1,2-S2-1,2-C2B10H10)(PPh3)2], [Au2(v-1,2-
S2-1,2-C2B10H10)(v-dppey)] ([5]a) [dppey=o-phenyl-
enebis(diphenylphosphino)] or in other dithiolate com-
plexes: [Au2(v-1,2-S2C6H4)(PPh3)2] [14], [Au2(v-3,4-
S2C6H3Me)(PPh3)2] [15], [Au2(v-MNT)(PPh3)2][MNT=
1,2-dicyanoethene-1,2-dithiolate] [16].
The presence in these compounds of the carborane
moiety is shown by a broad absorption at 2579 (6) and
2596 (7) cm−1 in their IR spectra, and a signal in their
1H-NMR spectra at about 3.8 ppm, assigned to the CH
proton. The signals corresponding to the methylene and
phenylic protons in these compounds are also present.
The two phosphorus atoms in the molecules are
equivalent, as only one signal is present in their
31P{1H}-NMR spectra.
˚
The AuꢀS distance, 2.3071(11) A, is of the same
order as that found in complexes mentioned above or
in [Au2{v-1,2-S2(CH2)3}(v-dppm)] [15] [v-dppm=bis-
(diphenylphosphinomethane)] and [Au2(v-MNT)(v-
dppey)2] [17], which contain related bridging ligands.
No short contacts are observed between gold atoms,
probably because of the bulky nature of the two carbo-
rane groups.
Although the molecular peaks [M]+ appear in the
positive ion mass spectra (FAB+) of complexes 6 and 7
[m/z=1142 (6%) (6), 1178 (4%) (7)], the most intense
are those corresponding to [M-(SC2B10H1)]+ [968 (6),
882 (7)].
We have also carried out the reaction of 1-(SH)-1,2-
C2B10H11 with [N(PPh3)2][AuCl2] and excess of Na2CO3
in the molar ratio 2:1, obtaining the anionic compound
[N(PPh3)2][Au(1-S-1,2-C2B10H11)2] (see Scheme 1). The
IR spectrum of this compound shows the bands from
the BꢀH stretching modes of the o-carborane nucleus at
Table 1
˚
Selected bond lengths (A) and angles (°) for 6
˚
Bond lengths (A)
Au(1)ꢀP(1)
P(1)ꢀC(11)
P(1)ꢀC(5)
2.2621(9)
1.811(4)
1.825(3)
Au(1)ꢀS(1)
P(1)ꢀC(21)
S(1)ꢀC(1)
2.3071(11)
1.816(3)
1.787(4)
2591 cm−1
.
1
The H-NMR spectrum of this derivative shows the
singlet assigned to the CH proton, and also the broad
signal due to the phenylic protons.
Bond angles (°)
P(1)ꢀAu(1)ꢀS(1)
C(1)ꢀS(1)ꢀAu(1)
176.06(3)
106.49(13)
C(5)ꢀP(1)ꢀAu(1) 114.32(12)
In the FAB-MS spectrum, the most intense peak is
assigned to the molecular anion [M]− (m/z=547).

4
M.M. Artigas et al. / Journal of Organometallic Chemistry 561 (1998) 1–6
Table 2
3.1. Syntheses
Atomic coordinates (×104) and equivalent isotropic displacement
2
3
˚
parameters (A ×10 ) for 6
3.1.1. [Au(1-S-1,2-C2B10H11)L] [L=PPh3 (1), PPh2Me
(2), SPPh3 (3), AsPh3 (4)]
x
y
z
Ueq
26(1)
To a solution of 1-(SH)-1,2-C2B10H11 (0.017 g, 0.1
mmol) in dichloromethane (30 cm3) [AuClL] was added
(0.1 mmol; 0.049 g L=PPh3; 0.043 g L=PPh2Me;
0.054 g L=SPPh3; 0.053 g L=AsPh3) and excess
Na2CO3. The mixture was stirred for 30 min, excess
Na2CO3 filtered off and the solution concentrated to ca.
5 cm3. Addition of diethyl ether (10 cm3) gave com-
plexes 1–4 as white solids. 1: yield 81%. Anal. Calc. for
C20H26AuB10PS: C, 37.85; H, 4.1. Found: C, 38.35; H,
Au(1)
P(1)
S(1)
C(1)
C(5)
4334(1)
4363(1)
4368(2)
4354(5)
4266(5)
2600(4)
2095(5)
804(6)
2742(1)
1538(1)
4097(1)
3230(4)
−83(3)
1184(3)
2178(4)
1982(5)
792(4)
−208(5)
−14(4)
2388(3)
3654(4)
4292(4)
3686(4)
2436(4)
1786(4)
2193(5)
1566(5)
2749(5)
4106(5)
3763(5)
3592(5)
2385(5)
998(5)
4608(1)
5771(1)
3525(1)
2268(3)
5203(3)
6236(3)
6449(3)
6854(4)
7020(3)
6806(4)
6412(3)
7015(3)
7175(3)
8125(3)
8899(3)
8748(3)
7805(3)
2201(4)
1587(4)
1083(4)
1384(4)
2043(4)
646(4)
20(1)
44(1)
29(1)
23(1)
24(1)
34(1)
43(1)
40(1)
41(1)
35(1)
22(1)
31(1)
37(1)
35(1)
39(1)
33(1)
36(1)
35(1)
36(1)
36(1)
37(1)
37(1)
39(1)
39(1)
40(1)
39(1)
37(1)
118(6)
101(1)
120(2)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
B(2)
B(3)
B(4)
B(5)
B(6)
B(7)
B(8)
B(9)
1(5)
466(5)
1
4.05. LM 4 V−1 cm2 mol−1. H-NMR, l ppm: 3.87 (s,
1775(5)
6355(4)
7597(5)
9139(5)
9437(5)
8186(5)
6645(5)
5316(6)
3042(6)
2628(7)
4559(6)
6217(6)
5642(7)
6111(7)
4112(6)
2405(7)
3360(7)
4301(6)
−621(24)
354(6)
1H, CH), 7.3–7.6 (m, br, 15H). 31P{1H}-NMR, l ppm:
36.8 (s). 2: yield 74%. Anal. Calc. for C15H24AuB10PS:
C, 31.45; H, 4.2. Found: C, 31.7; H, 4.7. LM 2 V−
1
1 cm2 mol−1. H-NMR, l ppm: 3.85 (s, 1H, CH), 2.05
[d, 3H, PMe, J(PH) 9.90 Hz], 7.4–7.7 (m, br, 10H).
31P{1H}-NMR, l ppm: 21.4 (s). 3: yield 74%. Anal.
Calc. for C20H26AuB10PS2: C, 36.05; H, 3.95;. Found:
1
C, 36.25; H, 3.8. LM 5 V−1 cm2 mol−1. H-NMR, l
ppm: 3.63 (s, 1H, CH), 7.3–7.6 (m, br, 15H). 31P{1H}-
NMR, l ppm: 43.9 (s). 4: yield 78%. Anal. Calc. for
C20H26AsAuB10S: C, 35.4; H, 3.85. Found: C, 35.9; H,
1149(4)
861(4)
162(4)
1
4.1. LM 2 V−1 cm2 mol−1. H-NMR, l ppm: 3.88 (s,
1H, CH), 7.3–7.6 (m, br, 15H).
B(10)
B(11)
B(12)
C(99)
Cl(1)
Cl(3)
1352(5)
2950(5)
1870(5)
4663(20)
3923(4)
6348(4)
44(4)
−112(4)
5102(17)
4359(4)
4969(5)
3.1.2. [Au2(1-S-1,2-C2B10H11)(PPh3)2]BF4 (5)
To a solution of 1-(SH)-1,2-C2B10H11 (0.017 g, 0.1
mmol) in dichloromethane (30 cm3) [O{Au(PPh3)}3]BF4
(0.149 g, 0.1 mmol) was added. The mixture was stirred
for 30 min. Concentration of solvent to ca. 5 cm3 and
addition of diethyl ether (10 cm3) afforded complex 5 as
389(7)
Ueq is defined as one third of the trace of the orthogonalised Uij
tensor.
a
white solid. Yield 56%. Anal. Calc. for
C38H41Au2B11F4P2S2: C, 38.65; H, 3.5. Found: C, 39.1;
3. Experimental
H, 3.85. LM 138 V−1 cm2 mol−1 1H-NMR, l ppm:
.
3.98 (s, 1H, CH), 7.3–7.5 (m, br, 30H). 31P{1H}-NMR,
l ppm: 35.6 (s).
IR spectra were recorded in the range 4000–200
cm−1 on a Perkin-Elmer 883 spectrophotometer using
Nujol mulls between polyethylene sheets. Conductivi-
ties were measured in ca. 5×10−4 mol dm−3 solu-
tions with a Philips 9509 conductimeter. C and H
analyses were carried out with a Perkin-Elmer 2400
microanalyser. MS spectra were recorded on a VG
autospec, with the FAB technique, using nitrobenzyl
alcohol as matrix. NMR spectra were recorded on a
Varian Unity 300 spectrometer and a Bruker ARX
300 spectrometer in CDCl3. Chemical shifts are cited
relative to SiMe4 (1H, external) and 85% H3PO4 (31P,
external).
1-(SH)-1,2-C2B10H11 was synthesised from o-carbo-
rane [11] (Desxil Chemical), dppe, dppp were Aldrich
analytical reagent grade and were used as-given. The
starting materials [AuClL] [18], [N(PPh3)2][AuCl2] [19]
and [O{Au(PPh3)}3]BF4 [20] were prepared by pub-
lished procedures.
3.1.3. [Au(1-S-1,2-C2B10H11)2(v-PP)] [PP=dppe (6),
dppp (7)]
To a dichloromethane solution (20 cm3) of [Au(1-S-
1,2-C2B10H11)(AsPh3)] (0.175 g, 0.2 mmol) dppe (0.039
g, 0.1 mmol) or dppp (0.041 g, 0.1 mmol) were added
and the solution was stirred for 30 min. The solvent
was removed in vacuo and addition of diethyl ether (10
cm3) gave complexes 6 and 7, respectively, as white
solids. 6: yield 89%. Anal. Calc. for C30H46Au2B20P2S2:
C, 31.5; H, 4.05. Found: C, 31.4; H, 3.7. LM 2 V−1
1
cm2 mol−1. H-NMR, l ppm: 3.90 (s, 1H, CH), 2.62
(br), 7.3–7.6 (m, br, 20H). 31P{1H}-NMR, l ppm: 34.4
(s). 7: yield 81%. Anal. Calc. for C31H48Au2B20P2S2: C,
32.2; H, 4.2. Found: C, 31.8; H, 4.2. LM 6 V−1
cm2 mol−1
.
1H-NMR, l ppm: 1.86 [q, 2H, CH2,
J(HH)=7.5 Hz], 2.73 (m, br), 3.80 (s, 1H, CH), 7.4–
7.7 (m, br, 10H). 31P{1H}-NMR, l ppm: 32.7 (s).

M.M. Artigas et al. / Journal of Organometallic Chemistry 561 (1998) 1–6
5
3.1.4. [N(PPh3)2][Au(1-S-1,2-C2B10H11)2] (8)
76344 Eggenstein-Leopoldshafen, Germany. Any re-
quest for this material should quote a full literature
citation and the reference number CSD-406885.
To a solution of 1-(SH)-1,2-C2B10H1 (0.035 g, 0.2
mmol) in dichloromethane (30 cm3) [N(PPh3)2][AuCl2]
(0.081 g, 0.1 mmol) and excess Na2CO3 were added.
The mixture was stirred for 30 min and excess Na2CO3
filtered off. Concentration of the solution to ca. 5 cm3
and addition of diethyl ether (10 cm3) afforded complex
8 as a white solid. Yield 77%. Anal. Calc. for
C40H52AuB20NP2S2: C, 44.25; H, 4.8; N, 1.8. Found: C,
Acknowledgements
We thank the Direccio´n General de Investigacio´n
Cient´ıfica y Te´cnica (No. PB94-0079), the Caja de
Ahorros de la Inmaculada (No. CB9/96) and the Fonds
der Chemischen Industrie for financial support.
44.25; H, 4.8, N, 2.25. LM 136 V−1 cm2 mol−1. H-
1
NMR, l ppm: 3.93 (s, 1H, CH), 7.3–7.5 (m, br, 20H).
31P{1H}-NMR, l ppm: 21.7 (s).
3.2. Crystal structure determination of complex 6
References
3.2.1. Crystal data
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clinic, space group P1, a=9.0242(12), b=11.4065(12),
˚
c=13.4348(12) A, h=100.563(8), i=107.089(8), k=
3
˚
111.992(8)°, V=1156.6(2) A , Z=1, Dcalc. =1.763
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631.
Mg m−3, u(Mo–Kh)=0.71073 A, v=6.637 mm
,
−1
˚
F(000)=588, T= −100°C.
3.2.2. Data collection and reduction
Single crystals were obtained by a slow diffusion of
di-isopropyl ether into a dicloromethane solution of
complex 6. A colourless plate 0.45×0.30×0.20 mm
was used to collect 8391 intensities to 2qmax 55°
(Siemens P4 diffractometer, monochromated Mo–Kh
radiation) of which 4711 were independent (Rint
=
0.0223). Cell constants were refined from 2q values of
63 reflections in the range 9–25°. An absorption correc-
tion was applied on the basis of C-scans (transmission
factors 0.531–1.000).
[5] (a) O. Crespo, M.C. Gimeno, P.G. Jones, B. Ahrens, A. Laguna,
Inorg. Chem. 36 (1997) 495. (b) O. Crespo, M.C. Gimeno, P.G.
Jones, A. Laguna, J. Chem. Soc. Dalton Trans. (1992) 1601. (c)
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3.2.3. Structure solution and refinement
The structure was solved by the heavy-atom method
and refined on F2 using the program SHELXL-93 [21].
Au, P, S, Cl and C atoms (except the carbon of the
solvent, which is disordered over a symmetry centre)
were refined anisotropically. The second C atom of the
carborane could not be distinguished from the remain-
ing B atoms; it is probable that there is fivefold disor-
der, with one C and four B atoms distributed at
random. Hydrogen atoms were included using a riding
model. wR(F2) 0.0547 for 4711 reflections, 220 parame-
ters and 40 restraints. Conventional R(F) 0.0235. S(F2)
−3
˚
0.979. Dz=1.550 e A
.
4. Supplementary material available
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Johnson, F.A. Gomez, M.F. Hawthorne, Inorg. Chem. 35 (1996)
5417.
Full details of structure determination (except struc-
ture factors) have been deposited at the Fachinforma-
tionszentrum
Karlsruhe,
Gesellschaft
fu¨r
Wissenschaftlich-technische Information mbH, D-

6
M.M. Artigas et al. / Journal of Organometallic Chemistry 561 (1998) 1–6
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.