Gold-ruthenium compounds containing bridging phosphide or thiolate groups: Crystal structures of the intermediate species [Ru3(CO)8L(μ3-η2,η4,η3-{Me3SiCC(C2Fc)SC(Fc)CS

Article abstract of DOI:10.1016/j.jorganchem.2006.05.008

New tetranuclear complexes have been prepared using bridging phosphide or thiolate groups between phosphine gold fragments and the compound [Ru₃(CO)₉(μ₃-η²,η⁴,η³-{Me₃SiCC(C₂

Full text of DOI:10.1016/j.jorganchem.2006.05.008

Journal of Organometallic Chemistry 691 (2006) 3596–3601
www.elsevier.com/locate/jorganchem
Gold–ruthenium compounds containing bridging phosphide or thiolate
groups: Crystal structures of the intermediate species
[Ru3(CO)8L(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})]
(L = NMe3 or PPh2H)
a,
a
b
a
a
*
´
Esther Delgado , Elisa Hernandez , Miguel A. Maestro , Angel Nievas , Maria Villa
a
Departamento de Quı´mica Inorga´nica, Facultad de Ciencias, Universidad Auto´noma de Madrid, 28049 Madrid, Spain
b
Departamento de Quı´mica Fundamental, Facultade de Ciencias, Universidad da Corun˜a, 15071 A Corun˜a, Spain
Received 28 March 2006; received in revised form 4 May 2006; accepted 5 May 2006
Available online 30 June 2006
Dedicated to Dr. J. Antonio Abad in occasion of his retirement.
Abstract
New tetranuclear complexes have been prepared using bridging phosphide or thiolate groups between phosphine gold fragments and
the compound [Ru3(CO)9(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})]. The crystal structures of the intermediates
[Ru3(CO)8(NMe3)(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})] and [Ru3(CO)8(PPh2H)(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)-
CSC„CSiMe3})] have been solved.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ruthenium carbonyls; Gold–ruthenium compounds; Triruthenium complexes
1. Introduction
are aware, the recently reported cluster compound Os3Au-
(CO)11(l-PPh2)PPh3 [3] is the only example containing a
bridging phosphide, while no derivatives have been
described containing a thiolate bridge. In this paper we
report the studies carried out on the compound
[Ru3(CO)9(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSi-
Me3})] in order to prepare new gold–ruthenium com-
pounds containing PPh2 as well as SR (R = Et, Ph)
bridging ligands. In addition to the analytical and spectro-
scopic data of the new complexes, crystallographic data
on the intermediate derivatives [Ru3(CO)8L(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})] (L = NMe3 or
PPh2H) are also reported.
Mixed-metal compounds may exhibit an interesting
chemistry from the point of view of organic synthesis, as
a consequence of synergic interactions among the different
metals. Many examples of polynuclear complexes contain-
ing mixed metals have been reported and among them,
clusters of Group 8 metals bonded to the AuPPh3 fragment
have been prepared by the reaction of ionic complexes with
the electrophilic fragment AuPPhþ3 . Thus, we have
obtained the clusters FexAu(CO)9(l-SR)PPh3 (x = 2 or 3;
R = alkyl or aryl group) [1] and Fe3Au(CO)9(l-
C„CR)PPh3 (R = Fc, But) [2] following this approach.
However gold fragments attached to polynuclear com-
pounds of the iron triad towards bridging phosphide or
thiolate groups are almost unknown. In fact, as far as we
2. Results and discussion
Secondary phosphines PR2H or PRR0H exhibit very
reactive P–H bonds and as a consequence they may
undergo easy deprotonation reactions affording phosphide
*
Corresponding author. Tel.: +34 914975268; fax: +34 914974833.
E-mail address: esther.delgado@uam.es (E. Delgado).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.05.008

E. Delgado et al. / Journal of Organometallic Chemistry 691 (2006) 3596–3601
3597
groups. Thus, it has been recently described [3] that the
deprotonation of the phosphine PPh2H in the cluster
Os3(CO)11PPh2H followed by the reaction of different
metal halides, allows the addition of MLn fragments to
the molecule. In order to establish whether this synthetic
method could be useful in our case, we have initially
prepared the phosphine derivative of compound
[Ru3(CO)9(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSi-
Me3})] (1). Among the few examples reported of polynu-
should take place. The ruthenole entity is made up of the
Ru2(CO)6 fragment and a C4 ligand showing a r, p coordi-
nation mode. The organic group forms a ruthenacyclopent-
adiene which is bonded to the other ruthenium atom.
Treatment of the triruthenium compound 1 with ONMe3
in toluene led to CO2 evolution and formation of new com-
pound [Ru3(CO)8(NMe3)(l3-g2,g4,g3-{Me3SiCC(C2Fc)-
SC(Fc)CSC„CSiMe3})] (2) (Scheme 1).
The presence of NMe3 ligand was inferred from 1H
NMR spectroscopy. Thus, the resonance at 2.79 ppm, in
the range observed for other amine derivatives [8], was
assigned to the methyl group of the NMe3 ligand. Addition-
ally, the IR spectrum in the carbonyl region [2096 (vw),
2071 (m), 2034 (vs), 2020 (m), 2002 (sh), 1998 (m)] is mod-
ified in comparison to the one that shows the precursor
[Ru3(CO)9(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„
CSiMe3})] [9]. The molecular peak (m/z 1264) as well as the
corresponding to the sequential loss of eight CO ligands
observed in the FAB-mass spectrum seem to suggest that
the substitution of one CO by one NMe3 has taking place.
clear derivatives containing
a
PPh2H ligand, the
compounds [HMCo3(CO)11(PPh2H) (M = Fe or Ru)
[4], Ru3(l-H)(l-N@CPh2)(PPh2H)(CO)9 [5], Os3(CO)9-
(l-dppm)(PPh2H) [6] and Os3Ru(CO)11(l-PPh2)(l-H)3-
PPh2H [7] have been prepared by direct decarbonylation
or substitution of labile ligands. The substitution of CO
by NMe3 requires mild conditions avoiding the degrada-
tion of polynuclear species. As compound 1 consists of a
ruthenole group joined to one Ru(CO)3 fragment towards
a dithioether, an additional aspect of interest for us was
to determine in which metal fragment the substitution
Fe
S
C
C
SiMe3
C
C
C
.
.
.
S
Ru
i
C
.
C . . C
Me3Si
Ru
Ru
Fe
.
.
Fe
SiMe3
C
C
S
S
Fe
C
C
.
SiMe3
(1)
C
C
C
C
C
PPh2H
NMe3
.
Ru
S
Ru
S
.
.
.
C
.
C
C
.
ii
.
C. . C
Me3SiC
C
.
Me3Si
Fe
Ru
Ru
Ru
.
Fe
Ru
.
.
.
.
.
(3)
(2)
iii
iv
Fe
SiMe3
C
SiMe3
C
C
C
S
Fe
S
Ph2
P
.
R'
S
.
C
C
C
C
.
C
AuPPh3
AuPR3
Ru
S
Ru
S
.
.
C
C
C
.
.
Me3SiC
C
.
Me3SiC
C
.
.
Fe
Fe
Ru
Ru
Ru
Ru
.
.
.
.
.
.
R= Ph (4), iPr (5)
R'= Et (6),Ph (7)
.
=CO
i= ONMe3, Toluene, r.t., 1h; ii= PPh2H, Toluene, r.t., 2.5h
iii=AuClPR3,DBU, TlBF4, Cl2CH2, r.t., 2h; iv= Au(SR')PPh3, Toluene, r.t., 1.5h
Scheme 1.

3598
E. Delgado et al. / Journal of Organometallic Chemistry 691 (2006) 3596–3601
The reaction of compound 2 with the stoichiometric
amount of PPh2H led to the formation of compound
[Ru3(CO)8(PPh2H)(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)-
CSC„CSiMe3})] (3), with IR spectrum in the carbonyl
region similar to the one of the amine precursor. The pres-
ence of the coordinated PPh2H ligand was confirmed by a
single resonance in the 31P NMR spectrum at 15.7 ppm.
The peak corresponding to the parent ion (m/z 1391)
appears in its FAB+ mass spectrum.
The proposed structures for compounds 2 and 3 on the
bases of analytical and spectroscopic data have been con-
firmed by X-ray diffraction methods (Figs. 1 and 2).
[Ru3(CO)8(NMe3)(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)-
CSC„CSiMe3})] (2) is one of the rare examples of clusters
containing the amine ligand being crystallographically
determined. The scarcity of this type of derivatives, formed
by extrusion of CO using ONMe3 as initiator showing sta-
bility in solid state maybe due to the lability of the NMe3
ligand.
A dichloromethane solution of compound 3 was treated
at room temperature with AuPPh3Cl and TlBF4, as
chloride abstractor, in the presence of DBU, leading after
2 h to compound [AuRu3(CO)8(l-PPh2)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3}PPh3)] (4). This
formulation is in accord with the spectroscopic data. A
Fig. 2. View of the crystal structure of compound 3. Selected bond distances
˚
(A) and angles (ꢁ). Ru(1)ARu(2) 2.7060(8), Ru(3)AS(1) 2.4458(18),
Ru(3)AP(1) 2.3548(18), C(1)AC(2) 1.403(9), C(2)AC(3) 1.432(10),
C(3)AC(4) 1.402(10), C(5)AC(6) 1.339(9), C(7)AC(8) 1.189(10),
C(6)AS(2)AC(7) 104.2(3), C(3)ARu(3)AP(1) 169.8(2), C(2)AS(1)AC(5)
95.6(3).
2
doublet resonance that appears at 32.1 ppm, with a JP–P
coupling of 255 Hz in 31P{1H} NMR is assigned to a bridg-
ing PPh2 group between the ruthenium and gold atoms
while a second doublet at 44.8 ppm (2JP–P = 255 Hz) has
been assigned to the presence of the AuPPh3 group. By
comparison, the compound [Au(C6F5)3(l-PPh2)AuPPh3]
shows in the 31P{1H} NMR spectrum resonances at 31.1
and 44.6 ppm for the PPh2 and PPh3, respectively, [10].
Although the molecular ion was not observed in the
FAB+ or MALDI mass spectra, a peak at m/z = 459
confirmed the presence of the AuPPhþ3 fragment in the
complex. The reaction using the AuPiPr3þ fragment yielded
the analogous compound [AuRu3(CO)8(l-PPh2)(l3-g2,
g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3}PiPr3)] (5). As
can be observed the higher steric hindrance of the iPr group
does not affect the outcome of this reaction.
Since the phosphide and thiolate groups are isoelec-
tronic, we considered of interest to study the possibility
of joining the AuPPhþ3 fragment to the [Ru3(CO)9-
(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})] (1)
using the metalloligands AuSRPPh3 (R = Et, Ph). Thus,
treatment of [Ru3(CO)8(NMe3)(l3-g2,g4,g3-{Me3SiCC-
(C2Fc)SC(Fc)CSC„CSiMe3})] (2) with the stoichiometric
amount of AuSRPPh3 in toluene at room temperature
afforded to compounds [AuRu3(CO)8(l-SR)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})PPh3] [R = Et (6);
Ph (7)]. Both complexes have been characterized by analyt-
ical and spectroscopic techniques. Resonances correspond-
ing to the organic groups (Et, Ph, SiMe3, Fc) present in
Fig. 1. View of the crystal structure of compound 2. Selected bond
distances (A) and angles (ꢁ). Ru(2)ARu(3) 2.7024(6), Ru(1)AS(2)
2.4708(12), Ru(1)AN(1) 2.289(4), C(3)AC(4) 1.444(6), C(4)AC(5)
1.407(6), C(3)AC(6) 1.419(6), C(17)AC(18) 1.199(6), C(1)AC(2) 1.345(6),
C(2)AS(1)AC(17) 105.2(2), C(1)AS(2)AC(4) 93.34, C(3)ARu(1)AN(1)
167.54(16) 167.54(6).
˚

E. Delgado et al. / Journal of Organometallic Chemistry 691 (2006) 3596–3601
3599
these molecules have been assigned in their 1H NMR spec-
tra. The IR pattern in the carbonyl region is similar in
both compounds and related to complexes [AuRu3-
(CO)8(l-PPh2)(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„
CSiMe3}-PPh3)] (4) and [AuRu3(CO)8(l-PPh2)(l3-g2,
g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3}PiPr3)] (5).
pounds containing the ruthenol fragment [Ru3(CO)9-
(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})] [9]
and [Ru4Ni(CO)12(l-PPh2)2(l4ꢀg1,g1,g2,g4-ButC„CC4C
„CBut)] [11]. The substitution of the one CO ligand by
amine or phosphine seems not to affect to the SARu
˚
˚
distance [2.4708(12) A for 2 and 2.4458(18) A for 3] in
comparison with the parent compound [Ru3(CO)9(l3-
g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})][2.4414
2.1. Crystal structures determination
˚
(10) A]. Angles of 167.54(16)ꢁ for C3ARu1AN1 in com-
pound 2 and 169.8(2)ꢁ for C3ARu3AP1 in 3 are in agree-
ment with the substitution of the CO in position trans to
one C atom of the ruthenol unit present in [Ru3(CO)9
(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3}). The
C(3)AC(4) 1.444(6), C(4)AC(5) 1.407(6) and C(3)AC(6)
The molecular structures of compound 2 and 3 are
depicted in Figs. 1 and 2. Crystal data and structure refine-
ment parameters are listed in Table 1. The selected bond
lengths and angles are collected as figure captions. The core
of the two compounds is similar. It contains the units
Ru2(CO)6 and Ru(CO)2L (L = NMe3 or PPh2H) linked
towards a polycarbon sulfur chain. A pseudo-octahedral
geometry is located around each of the ruthenium atoms.
The crystallographic data of 2 and 3 reveal the structure
arising from the substitution of one CO ligand in the
metalAmetal unbonding Ru(CO)3 fragment of the precur-
sor 1, by an amine or phosphine ligand in position trans to
the carbon atom of the ruthenol group towards it is linked.
1.419(6) distances for compound
2 and C(1)AC(2)
1.403(9), C(2)AC(3) 1.432(10) and C(3)AC(4) 1.402(10)
for 3 are in the range expected for a ruthenol unit. A value
˚
of 1.199(6) A for the C(17)AC(18) distance observed in
˚
compound 2 and 1.189(10) A for C(7)AC(8) in 3, confirm
the presence of a free alkynethiolate group in both
molecules.
3. Experimental
˚
The RuARu bond distances of [2.7024(6) A] in 2 and
˚
[2.7060(8) A] 3 are comparable with those found in com-
All reactions were carried out under argon atmosphere
using Schlenk techniques. Solvents were dried according
to standard methods. IR spectra were recorded on a Per-
kin–Elmer 1650 FTIR spectrophotometer using NaCl cells.
1H NMR and 31P NMR spectra were registered on a Bru-
ker AMX-300 instrument. Elemental analyses were
performed on a Perkin–Elmer 240-B microanalyzer. FAB
mass spectra were carried out on a WG AutoSpec spec-
trometer, using 3-nitrobenzylalcohol as matrix. Me3SiC„
CSC„CFc [12], [AuClPPh3] [13] and [AuSRPPh3] [R = Et,
Ph] [14] were prepared as previously reported.
Table 1
Crystallographic data for compounds 2 and 3
Compound
Formula
2
3
C
45H45Fe2NO8
C54H47Fe2O8P
Ru3S2Si2
1390.10
012 · 0.06 · 0.03
Monoclinic
P21/c
Ru3S2Si2 Æ 0.5C6H14
1306.12
0.26 · 0.12 · 0.02
Triclinic
P1
2
12.0217(10)
13.4150(11)
18.1263(15)
80.380(2)
73.979(2)
72.073(2)
173(2)
2662.5(4)
1.629
1.54178
Fw
Crystal size (mm)
Crystal system
Space group
Z
ꢀ
4
˚
a (A)
17.4064(8)
13.2576(10)
25.4584(10)
90
98.051(2)
90
100(2)
5817.1(6)
1.587
11.798
2776
2.56–68.25
26,645
10,285 [0.0823]
3.1. Synthesis of [Ru3(CO)8(NMe3)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})] (2)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
A
mixture of [Ru3(CO)9(l3-g2,g4,g3-{Me3SiCC-
(C2Fc)SC(Fc)CSC„CSiMe3})] (1) (0.062 g, 0.051 mmol)
and ONMe3 (0.006 g, 0.079 mmol), was stirred in toluene
(15 ml), bubbling argon, during 1 h. The solvent was
removed and the amine derivative [Ru3(CO)8(NMe3)-
(l3-g2,g4,g3-{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3})] (2),
extracted with hexane from the residue (0.048 mmol, 93%
yield). Crystals of 2 were obtained in n-hexane at ꢀ20 ꢁC.
IR (hexane) cmꢀ1 mCO 2096 (vw), 2071 (m), 2034 (vs),
2020 (m), 2002 (sh), 1998 (m), 1980 (w), 1968 (m); 1H
NMR (CDCl3, 300 MHz, 22 ꢁC) d: 4.48–4.22 [m, 4H,
C5H4], 4.23 [s, 5H, C5H5], 4.17 [s, 5H, C5H5], 4.16–4.12
[m, 4H, C5H4], 2.79 [s, 9H, NMe3], 0.10 [s, 9H, SiMe3],
0.00 [s, 9H, SiMe3]. MS(FAB+) m/z 1264 (M++H), 1204
(M++H-NMe3), 1176–981 (M++H-NMe3-nCO, n = 1–8).
Anal. Calcd. for C45H45O8S2Si2NFe2Ru3 (Found): C,
42.76 (41.85); H, 3.56 (3.94); N, 1.11(1.07); S, 5.06
(4.81)%.
Temperature (K)
3
˚
Volume (A )
qcalc (g cmꢀ3
)
l (mmꢀ1
F(000)
)
1310
1.83–28.32
17,321
h Range (ꢁ)
Observed reflections
Independent
reflections [Rint
12,152 [0.0355]
]
Index ranges
ꢀ16 to 15,
ꢀ16 to 17,
ꢀ16 to 23
12,152/7781
0.963
ꢀ20 to 18,
ꢀ14 to 15,
ꢀ30 to 27
10,285/6269
0.906
Reflections collected/unique
Goodness-of-fit on F2
Largest difference
0.732 and ꢀ0.729
1.318 and ꢀ1.103
ꢀ3
˚
in peak/hole (e A
)
Final R indices [I > 2r(I)]
R1
wR2
0.0455
0.0806
0.0531
0.1159

3600
E. Delgado et al. / Journal of Organometallic Chemistry 691 (2006) 3596–3601
3.2. Synthesis of [Ru3(CO)8(PPh2H)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3})] (3)
CH(CH3)2), 1.25 (d, 9H, J = 7.1 Hz, CH(CH3)2), 0.12 (s,
9H, SiMe3), ꢀ0.09 (s, 9H, SiMe3). 31P{1H} NMR (CDCl3,
2
300 MHz, 22 ꢁC) d: 72.6 (d, PiPr3, JP–P: 247 Hz), 32.0 (d,
2
HPPh2 (0.008 ml, 0.047 mmol) was added to a solution
of compound 2 (0.06 g, 0.047 mmol) in toluene (20 ml).
The mixture was stirred while bubbling argon for 2.5 h at
room temperature and the solvent was evaporated to dry-
ness. The orange residue was washed several times with
cold hexane to afford to a solid compound corresponding
to compound [Ru3(CO)8(PPh2H)(l3-g2,g4,g3-{Me3SiCC-
(C2Fc)SC(Fc)CSC„CSiMe3})] (3) (0.029 mmol, 61%).
Crystals of 3 were obtained in CH2Cl2/n-hexane (1:2) at
ꢀ20 ꢁC. IR (hexane) cmꢀ1 mCO 2092 (vw), 2069 (m), 2040
(vs), 2023 (m), 1988 (s), 1976 (m). 1H NMR (CDCl3,
300 MHz, 22 ꢁC) d: 7.67–7.46 (m, 10H, C6H5), 6.51 (d,
1H, P–H, JH–P: 363.4 Hz), 4.34–4.20 (m, 4H, C5H4), 4.18
(s, 5H, C5H5), 4.12–4.10 (m, 4H, C5H4), 4.09 (s, 5H,
C5H5), ꢀ0.02 (s, 9H, SiMe3), ꢀ0.05 (s, 9H, SiMe3).
31P{1H} NMR (CDCl3, 300 MHz, 22 ꢁC) d: 15.3.
MS(FAB+) m/z 1391 (M++H), 1363–1167 (M++H-nCO,
n = 1–8), 1204 (M++H-PPh2H). Anal. Calcd. for
C54H47O8S2Si2PFe2Ru3 (Found): C, 46.66 (46.69); H,
3.38 (4.11); S 4.61 (4.28)%.
PPh2, JP–P: 247 Hz). MS(FAB+) m/z: 1522 (M+ꢀ8CO),
543 (HPPh2AuPiPr3), 357 (AuPiPr3). Anal. Calcd. for
C63H67O8S2Si2P2Fe2Ru3Au Æ 1/2CH2Cl2 (Found): C, 42.64
(42.57); H, 3.80 (3.87); S 3.58 (3.53)%.
3.5. Synthesis of [AuRu3(CO)8(l-SEt)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3}PPh3)] (6)
AuSEtPPh3 (0.012 g, 0.023 mmol) was added to a solu-
tion of compound 2 (0.028 g, 0.022 mmol) in toluene
(10 ml). The mixture was stirred while bubbling argon for
1.5 h at room temperature and the solvent was evaporated
to dryness. Compound [AuRu3(CO)8(l-SEt)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSC„CSiMe3}PPh3)] (6) was
obtained as red crystals from Cl2CH2/hexane (1:3) at
ꢀ20 ꢁC (0.018 g, 0.01 mmol, 47.5% yield). IR (hexane)
cmꢀ1 mCO 2092 (vw), 2068 (s), 2028 (vs), 2030 (vs), 2016
(s), 1998 (sh), 1992 (s), 1961 (m), 1907 (vw). 1H NMR
(CDCl3, 300 MHz, 22 ꢁC) d: d 7.65–7.50 (m, 10H, C6H5),
4.45–4.33 (m, 3H, C5H4), 4.19 (s, 5H, C5H5), 4.16–4.04
(m, 5H, C5H4), 4.11 (s, 5H, C5H5), 3.13 (m, 2H, CH2CH3),
1.56 (t, 3H, J = 7.24 Hz, CH2CH3), 0.01 (s, 9H, SiMe3),
ꢀ0.01 (s, 9H, SiMe3). 31P{1H} NMR (CDCl3, 300 MHz,
22 ꢁC) d: 37.2 (s, PPh3). MS(FAB+) m/z: 1584–1500
(M+ꢀnCO, n = 5–8), 1472 (M+ꢀ8CO-Et), 520 (AuS-
EtPPh3), 459 (AuPPh3). Anal. Calcd. for C62H56O8S3Si2P-
Fe2Ru3Au Æ CH2Cl2 (Found): C, 41.83 (41.87); H, 3.21
(3.69); S 5.31(4.92)%.
3.3. Synthesis of [AuRu3(CO)8(l-PPh2)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3}PPh3)] (4)
A dichloromethane solution (10 ml) of compound 3
(0.02 g, 0.014 mmol) was treated with the stoichiometric
amount of DBU (0.002 ml, 0.015 mmol), followed of Au-
ClPPh3 (0.008 g, 0.015 mmol) and TlBF4 (0.004 g,
0.015 mmol). The mixture was stirred 2 h at room temper-
ature, the solvent was evaporated to dryness and the
residue crystallized from CH2Cl2/hexane at ꢀ20 ꢁC to
afford [AuRu3(CO)8(l-PPh2)(l3-g2,g4,g3-{Me3SiCC(C2Fc)-
SC(Fc)CSC„CSiMe3}PPh3)] (4) (0.008 mmol, 60%). IR
(hexane) cmꢀ1 mCO 2086 (vw), 2067 (m), 2028 (vs), 2014
(sh), 1991 (s), 1961 (m). 1H NMR (CDCl3, 300 MHz,
22 ꢁC) d: 7.91–7.43 (m, 25H, C6H5), 4.35–4.16 (m, 5H,
C5H4), 4.14 (s, 5H, C5H5), 4.08–3.92 (m, 3H, C5H4), 3.90
(s, 5H, C5H5), ꢀ0.11 (s, 9H, SiMe3), ꢀ0.14 (s, 9H, SiMe3).
31P{1H} NMR (CDCl3, 300 MHz, 22 ꢁC) d 44.8 (d, PPh3,
3.6. Synthesis of [AuRu3(CO)8(l-SPh)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3}PPh3)] (7)
Compound 7 was obtained following the above proce-
dure for 6. IR (hexane) cmꢀ1 mCO 2091 (vw), 2067 (m),
1
2034 (vs), 2019(s), 1992 (s), 1970 (m). H NMR (CDCl3,
300 MHz, 22 ꢁC) d: 7.59 (m, 15H, PPh3), 7.29 (m, 5H,
SPh), 4.42–4.24 (m,4H, C5H4), 4.16 (s, 5H, C5H5), 4.09–
3.93 (m, 4H, C5H4), 4.07 (s, 5H, C5H5), 0.00 (s, 9H, SiMe3),
ꢀ0.02 (s, 9H, SiMe3). 31P{1H} NMR (CDCl3, 300 MHz,
22 ꢁC) d: 37.1 (s, PPh3). MS(FAB+) m/z: 1548
(M+ꢀ8CO), 1208 (M+ꢀ8CO-Ph-PPh3), 568 (AuSPhPPh3),
459 (AuPPh3). Anal. Calcd. for C66H56O8S3Si2PFe2-
Ru3Au Æ 1/2CH2Cl2 (Found): C, 44.01 (43.98); H, 3.14
(3.57); S 5.29 (4.88)%.
2
2JP–P: 255 Hz), 32.1 (d, PPh2, JP–P: 255 Hz). Anal. Calcd.
for C72H61O8S2Si2P2Fe2Ru3Au Æ C6H14 (Found): C, 48.40
(48.03); H, 3.88 (4.10); S 3.31 (3.21)%.
3.4. Synthesis of [AuRu3(CO)8(l-PPh2)(l3-g2,g4,g3-
{Me3SiCC(C2Fc)SC(Fc)CSCCSiMe3}(PiPr3))] (5)
3.7. X-ray crystallographic studies
Compound 5 was prepared following the method
described for 4. The solid residue was purified by TLC
silica plates using hexane/CH2Cl2 (10:1) as eluent. IR (hex-
ane) cmꢀ1 mCO 2092 (vw), 2065 (m), 2032 (vs), 2017 (sh),
Data collection of compounds 2 and 3 were carried out
at 100 and 173 K, respectively, on a Bruker SMART-CCD
area diffractometer operating at 50 kV and 30 mA with
graphite monochromated Mo Ka radiation (k =
1
1991 (s), 1965 (m). H NMR (CDCl3, 300 MHz, 22 ꢁC) d:
7.83–7.30 (m, 10H, C6H5), 4.42–4.24 (m, 4H, C5H4), 4.17
(s, 5H, C5H5), 4.08 (s, 5H, C5H5), 4.07–3.92 (m, 4H,
C5H4), 2.36 (m, 3H, CH(CH3)2), 1.30 (d, 9H, J = 7.1 Hz,
˚
˚
0.71073 A) for 2 and Cu Ka radiation (k = 1.54178 A)
for 3.

E. Delgado et al. / Journal of Organometallic Chemistry 691 (2006) 3596–3601
3601
Crystal data and structure refinement parameters for
Acknowledgement
compounds 2 and 3 are listed in Table 1. The unit cell
parameters were refined from the observed positions of
all strong reflections in the complete data sets. Several sets
of frames of intensity data were collected over a hemi-
sphere of the reciprocal space by combination of exposure
sets. A 0.2% decay was observed for compound 2 and no
decay for 3.
´
We thank Ministerio de Ciencia y Tecnologıa of Spain
(Project BQU 2001/0216) for financial funding.
References
´
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Crystallographic data for compounds 2 and 3 have been
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the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
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