Synthesis of homo- and heteronuclear ruthenium-gold clusters with diphosphine and thiolato bridged ligands. Single crystal molecular structure of [Ru3(CO)10(μ-AuPPh3)(μ-SC 5H4N)] and [Ru3(C

Article abstract of DOI:10.1016/j.jorganchem.2010.11.034

The reaction between [Ru₃(CO)₁₀(NCMe)₂] and [AuClPPh₃] gave compound [Ru₃(CO)₁₀(μ- Cl)(μ-AuPPh₃)] (1) in quantitative yield under very mild conditions. The reaction of 1 with 4-m

Full text of DOI:10.1016/j.jorganchem.2010.11.034

Journal of Organometallic Chemistry 696 (2011) 2177e2185
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of homo- and heteronuclear rutheniumegold clusters with diphosphine
and thiolato bridged ligands. Single crystal molecular structure of
[Ru3(CO)10(m-AuPPh3)(m-SC5H4N)] and [Ru3(CO)8(m-H)(m-SC5H4N)(m-dppe)]
María G. HernándezeCruz a, Gloria SánchezeCabrera a, Micaela HernándezeSandoval a, Marco A. Leyva b,
María J. RosaleseHoz b, Berenice A. OrdoñezeFlores a, Verónica Salazar a, Alfredo Guevara Lara a,
,
Francisco J. Zuno-Cruz a
*
a Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Km 4.5 Carretera PachucaeTulancingo, Pachuca Hgo.,
42184 México, Mexico
b Departamento de Química, Centro de Investigación y Estudios Avanzados del I. P. N., Apdo. postal 14-740, 07000 México D. F., Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction between [Ru3(CO)10(NCMe)2] and [AuClPPh3] gave compound [Ru3(CO)10(m-Cl)(m-AuPPh3)]
Received 25 October 2010
Received in revised form
17 November 2010
(1) in quantitative yield under very mild conditions. The reaction of 1 with 4-mercaptopyridine (4-pyS)
using ultrasonic reaction conditions gave the heteronuclear compound [Ru3(CO)10 -AuPPh3)( -SC5H4N)]
(2) in moderate yield. There was no spectroscopic evidence that indicates the formation of the hydride
isolobal analog in this reaction. The homonuclear cluster [Ru3(CO)8( -H)( -SC5H4N)( -dppe)] (3) was
prepared by a selective reaction employing the rutheniumediphosphine derivative [Ru3(CO)10 -dppe)]
(dppe 1,2-bis(diphenylphosphine)ethane) with 4-pyS in THF solution. The isolobal analog to
compound 3, compound [Ru3(CO)8( -AuPPh3)( -SC5H4N)( -dppe)] (4) was synthesized by the reaction
(
m
m
Accepted 18 November 2010
m
m
m
(
m
Keywords:
¼
Homonuclear clusters
Heteronuclear clusters
Ruthenium
Gold
Sulfur
m
m
m
between compound 2 and dppe in refluxing dichloromethane. Compounds 1e4 were characterized in
solution by spectroscopic methods and the molecular structure of compounds 2 and 3 in the solid state
was obtained by single crystal X-ray diffraction studies.
Mercaptopyridine
Diphosphine
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
metal carbonyl cluster involving different types of ligands with
main group heteroatoms linked to the metal core with unique
Hetero- and homometallic transition metal clusters have found
one of its applications in the field of catalysis, due to the develop-
ment of better and more selective processes to prepare carbonyl
clusters. The potential advantage of cluster compounds is related to
the fact that several metal atoms linked together can provide
specific sites of interaction or cooperative reactivity between
substrate and cluster [1,2]. In the case of heterometallic clusters, it
has been suggested that the inert polarity of heterometallic bond
can direct the selectivity of substrateecatalyst interactions [1,3].
It has been report that a RueAu cluster catalytically isomerizes
1-pentene to cis and trans-2-pentene and under the same condi-
tions; the mixed metal cluster is more active than homometallic
ruthenium cluster [4]. One of the challenges over the past few
years has been the synthesis of homo- and heteronuclear transition
catalytic properties [3,5e8]. Of the many potential applications that
these types of compounds could have, the hydrodesulfurization
process (HDS), to remove sulfur from organosulfur compounds
presents in petroleum distillates, has a great deal of industrial
relevance [1,9,10].
There are several synthetic methods to prepare heteronuclear
compounds described in the literature [11,12]. One of them involves
oxidative addition reactions using the complexes [MX(PR3)]
(M ¼ Cu. Ag, Au; X ¼ Cl, Br, I, Me; R ¼ alkyl or aryl) to introduce an
M(PR3) fragment into a neutral cluster precursor [12]. Through this
methodology, it has been possible to synthesize compounds like
[Ru5C(CO)15
[13]. Using this method, the cluster [Ru3(CO)10
was originally prepared from [Ru3(CO)12 and [AuClPPh3] in
(m-AuPPh3)Cl] from the neutral carbonyl parent clusters
(m
-Cl)( -AuPPh3)]
m
]
refluxing dichloromethane for 18 h, in 55% yield. This compound
has shown to have low stability and decomposes in refluxing cyc-
lohexane to yield [Ru3(
[Ru3(CO)10 -Cl)( -AuPPh3)] can only be accessed under very mild
conditions [14].
m-Cl)2(CO)8(PPh3)2]; hence, the compound
* Corresponding author. Tel.: þ52 771 7172000x2204, þ52 1771 1625212
(mobile); fax: þ52 771 7172000x6502.
(m
m
E-mail address: fjzuno@uaeh.edu.mx (F.J. Zuno-Cruz).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.11.034

2178
M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
On the other hand, some reactions of thiolato ligands with
were carried out. The molecular structures of compounds 2 and 3
in the solid state were determined by single crystal X-ray diffrac-
tion studies.
homonuclear ruthenium cluster compounds have been described.
The reactions of homonuclear triruthenium clusters with mercapto
ligands produce complexes with sulfur bridging metalemetal
bonds [15,16]; moreover, when the (pyrid-2-yl)thiolato ligand is
used in reactions with tri- and hexanuclear ruthenium clusters, the
2. Results and discussion
k
1-N coordination is observed alongside the S bridge one [15,17].
The quantitative synthesis of compound [Ru3(CO)10(m-Cl)(m-
Also, some studies of heterometallic rutheniumegold clusters
with sulfur and/or phosphine ligands have been carried out. For
example, the formation of a thiolato group bridging a ruthenium
and a gold atom, which are not bonded, has been described [18] and
the reactions between ruthenium clusters with bidentate diphos-
AuPPh3)] (1) was carried out by the treatment at room temperature
(r. t.) of a dichloromethane solution of [Ru3(CO)10(NCMe)2] with
1 equiv of [AuClPPh3] for 15 min, Scheme 1. The infrared spectrum
obtained was consistent with the previously described [14]. The
multinuclear NMR spectroscopic data for compound 1 are given in
Table 1.
phine gold ligands like [Au2(m-dppm)Cl2] have produced mixed
metal compounds where the diphosphine ligand remained
attached to the gold atoms [19,20]. However, there are no reports of
rutheniumegold cluster with both thiolato and bidentate phos-
phine ligands coordinated to the metallic skeletal fragment.
In a previous work, we described the synthesis of the osmium
The 31P{1H} NMR spectrum of compound 1, obtained at r. t.,
shows a singlet at 71.2 ppm assigned to the coordinated gold
phosphine group, the signal shows a set of satellites caused by
the coupling with 13C due to the Cipso with a 1J
coupling of
13Ce31
P
48.6 Hz, this set of satellites are unsymmetrically centered around
the signal. This is characteristic for an isotopomeric effect nD13/12C
(secondary isotope effects on the nuclear shielding of a signal),
a negative sign on this nD13/12C denotes a low frequency shift
with respect to the lighter isotope [22]; as a result measuring the
difference between the phosphorous signal and each one of the
satellites, it can be possible to calculate the Dd difference to
determine the isotopomeric effect 1D13/12C. The value found for
compound 1 was ꢀ43.4 ppb. The 13C{1H} NMR spectrum of 1 shows
four doublet resonances at 134.0, 131.4, 131.2 and 129.3 ppm cor-
responding to the Corto, Cpara, Cipso and Cmeta, of the phenyl rings
derivatives [Os3(CO)10
(m-Cl)(m-AuPPh3)] and [Os3(CO)10(m-AuPPh3)
(m-SC5H4N)] analogs to compounds 1 and 2 respectively [21].
As part of our ongoing studies in the synthesis of compounds
with potential application in catalysis, for instances in multiple
bond hydrogenations and/or HDS processes; in this paper, we
describe the synthesis of three new compounds [Ru3(CO)10
AuPPh3)( -SC5H4N)] (2), [Ru3(CO)10 -H)( -SC5H4N)( -dppe)] (3)
and [Ru3(CO)8( -AuPPh3)( -SC5H4N)( -dppe)] (4). Compounds 2
and 3 were obtained from the reactions of [Ru3(CO)10 -Cl)
-AuPPh3)] (1) or [Ru3(CO)10 -dppe)] with 4-mercaptopyridine
(m-
m
(m
m
m
m
m
m
(m
(m
(m
(4-pyS) respectively, and compound 4 was synthesized from 2 and
dppe. The conditions employed were moderately soft in all reac-
tions. We have also designed an alternative synthetic method to
of the AuPPh3 group, with nJ
respectively) and the carbonyl region spectra shows six signals due
to mirror symmetry in the molecule for the six different types of CO
groups (see structure in Fig. 1), similar to that found for analogous
coupling (n ¼ 2, 4, 1 and 3
13Ce31
P
obtain
1 in quantitative yield from the activated cluster
[Ru3(CO)10(NCMe)2] and [AuClPPh3] in dichloromethane at room
temperature. Compounds 1e4 were characterized in solution by
Infrared and 1H, 31P{1H} and 13C{1H} NMR spectroscopy. Full as-
signment of carbon atoms for all compounds was completed with
2-D heteronuclear correlation experiments; additionally, homo-
and heteronuclear irradiations experiments of 1H and 31P nucleus
osmium compound [Os3(CO)10(m-Cl)(m-AuPPh3)] [21]. Three singlet
resonances at 208.4 and 205.0 were assigned to CO(5,6), and the
singlet at 194.2 ppm was assigned to CO [4], these 3 CO groups are
bonded to the ruthenium atom not bonded to the AuPPh3 group,
a doublet resonance at 196.0 ppm, (3J
¼ 13.8 Hz), was
13Ce31
P
assigned to the CO(2) in trans position to the Au atom and the
Scheme 1. Synthesis of the rutheniumegold clusters 1e4.

M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
2179
Table 1
1H, 31P and 13C NMR data for 1e4.
n
o
n
o
Compound
1H
d
(ppm) J(Hz)
31P
d
(ppm) J(Hz) 1J
13C{1H}
d
(ppm) J(Hz) ½3J
Pꢁ 1J
134.0 (d) Co
13Ce31
P
13 Ce31
13 Ce31P
1
7.48 (m, 15H, Ph)
71.2 (s)
{48.6}
208.4 (s) CO
205.0 (s) CO
2J
¼ 14.6
13 Ce31
P
1D13/12C ¼ ꢀ43.4 ppb
203.6 (d) CO [2.3]
196.0 (d) CO [13.8]
194.2 (s) CO
191.2 (d) CO [2.3]
208.6 (s) CO
131.4 (d) Cp
4J
¼ 2.3
13 Ce31
P
131.2 (d) Ci {46.9}
129.3 (d) Cm [10.8]
134.0 (d) Co
2
3
7.50 (m, 15H, Ph)
8.31 (2H, HXX
7.36 (2H, HAA
73.0 (s)
{45.1}
2J
¼ 14.6
0
)
)
205.6 (s) CO
13 Ce31
P
1D13/12C ¼ ꢀ22.3ppb
204.9 (d) CO [3.8]
197.5 (d) CO [13.1]
194.1 (d) CO [2.3]
193.7 (s) CO
131.4 (d) Cp
4J
0
0
0
0
0
JAA ¼ 5.5, JXX ¼ 1.4, JAX,JA X ¼ 7.0
¼ 2.3
13 Ce31
P
131.2 (d) Ci {46.1}
129.4 (d) Cm [10.8]
127.7 (s) CHAA
0
157.8 (s) CeS
149.1 (s) CHXX
214.5 (dd) CO
7.79 (m, 2H, Ho1)
45.5 (s) P1
{48.6}
2J
¼ 10.0
13 Ce31
P
7.71 (m, 2H, Ho4)
7.55 (m, 3H, Hm4, Hp4)
7.52 (m, 3H, Hm1, Hp1)
2J
¼ 10.0, [3.8]
133.5 (d) Co4
2J
¼ 12.3
13Ce31
P
1D13/12C ¼ ꢀ42.4 ppb
209.3 (d) CO
2J
¼ 3.1
13 Ce31
P
44.4 (s) P2
{41.6}
131.3 (d) Cp1
4J
¼ 1.5
13Ce31
P
7.34 (m, 4H, Ho3, Hp2,3
7.30 (m, 2H, Hm3)
7.23 (m, 2H, Ho2)
7.20 (m, 2H, Hm2)
0
)
209.2 (d) CO
2J
13 Ce31
P
1D13/12C ¼ ꢀ43.7ppb
¼ 8.5
131.1 (d) Cp4
4J
13Ce31
P
201.0 (s, br) CO
198.8 (d) CO
¼ 1.5
13 Ce31
P
130.4 (d) Cm2 [9.2]
129.9 (d) Cm3 [10.0]
129.8 (s) Cp2,3 (2C)
8.11 (2H, HXX
)
)
2J
¼ 3.8
13Ce31
P
0
6.56 (2H, HAA
196.1 (s, br) CO
192.0 (d) CO
0
0
0
0
JAA ¼ 4.4, JXX ¼ 1.1, JAX,JA X ¼ 5.5
129.1 (d) Cm1,4 [10.0] (2C)
128.8 (d) Co3
2.62 (m, 2H, CH2)
2J
¼ 8.5
13Ce31
P
1.90 (m, 2H, CH2)
188.2 (s) CO
159.7 (s) CeS
148.4 (s) CHXX
140.2 (d) Ci2 {46.1}
138.2 (d) Ci3 {42.3}
134.2 (d) Ci1 {46.1}
134.1 (d) Ci4 {38.4}
133.9 (d) Co1
2J
¼ 10.0
13 Ce31
P
ꢀ15.00 (dd, 1H, MeHeM)
128.5 (d) Co2
2J
¼ 10.0
2J
¼ 34.6, 3
J
¼ 2.8
0
13 He31
P
13 He31
P
13 Ce31P
0
126.7 (s) CHAA
28.4 (dd) CH2 {30.0}
2J
¼ 6.2
13 Ce31
P
25.1 (dd) CH2 {26.9}
2J
¼ 3.8
13 Ce31
P
4
7.70 (m, 2H, Ho1)
7.68 (m, 2H, Ho4)
7.62 (m, 6H, Ho5)
69.8 (d) P3
217.4 (br) CO
130.9 (d) Cp5
4J
¼ 2.3
2J
¼ 41.6
214.4 (d) CO
13 Pe31
P
13 Ce31P
51.2 (d) P1
2J
2J
¼ 8.5
130.7 (d) Cp4
4J
¼ 2.3
13Ce31
P
7.47 (m, 8H, Hm4, Hp4, Hp5, Hm4 [2:1:3:2 ratio])
7.46 (m, 3H, Hm3, Hp3 [2:1 ratio])
7.42 (m, 3H, Hm1, Hp1 [2:1 ratio])
7.36 (m, 2H, Ho3)
7.34 (m, 4H, Hm5)
7.32 (m, 1H, Hp2)
7.22 (m, 2H, Ho2)
7.18 (m, 2H, Hm2)
8.00 (2H, HXX
6.71 (2H, HAA
¼ 41.6
213.5 (d) CO
2J
¼ 9.2
13 Pe31
P
13 Ce31P
47.0 (s) P2 {41.6}
130.5 (d) Cp1
4J
13Ce31
P
1D13/12C¼ ꢀ43.5 ppb
206.7 (d) CO
2J
¼ 3.1
¼ 2.3
13 Ce31
P
130.5 (d) Cm2 [9.2]
130.1 (d) Cm3 [10.0]
129.5 (d) Cp2
13Ce31
P
200.3 (d) CO
2J
¼ 3.1
13Ce31
P
200.2 (br) CO
198.7.0 (br) CO
197.6 (br) CO
159.2 (s) CeS
4J
¼ 2.3
13 Ce31
P
129.1 (d) Cp3
4J
0
)
)
¼ 2.3
13 Ce31
P
0
129.0 (d) Cm [10.8]
0
0
0
0
0
0
JAA ¼ 4.7, JXX ¼ 1.4, JAX,JA X ¼ 6.0
148.0 (s) CHXX
128.9 (s) CHAA
2.49 (m, 2H, CH2)
1.91 (m, 2H, CH2)
140.9 (d) Ci2 {42.3}
138.7 (d) Ci3 {42.3}
136.5 (d) Ci1 {43.8}
135.1 (d) Ci4 {39.2}
134.3 (d) Co5
128.8 (d) Cm4 [10.0]
128.6 (d) Cm1 [10.0]
128.5 (d) Co3
2J
¼ 9.2
13 Ce31
P
128.2 (d) Co2
2J
¼ 9.2
2J
¼ 15.4
13Ce31
P
13 Ce31P
134.2 (d) Co1
2J
¼ 10.8
28.5 (dd) CH2 {26.1}
2J
¼ 6.2
13Ce31
P
13 Ce31P
133.2 (d) Co4
2J
¼ 11.5
24.7 (dd) CH2 {26.1}
2J
¼ 3.8
13Ce31
P
13 Ce31P
132.3 (d) Ci5 {44.6}
(s) singlet, (d) doublet, (dd) doblet of doublet, (m) multiplet, (br) broad, o, ortho; p, para; m, meta; i, ipso.
doublet resonances at 203.6 and 191.2 ppm, with coupling
constants 3 of 2.3 Hz, were assigned to CO(1,3), in cis position
to the Au atom, Fig. 1.
A dichloromethane solution of compound 1 was treated at r. t.
with an equiv of 4-mercaptopyridine in an ultrasonic bath, leading
to a mixture of three products after 10 min. Separation by prepar-
ative thin-layer chromatography (TLC), gave as a major product
with Lavigne and coworkers [14]. A third product obtained could
not be identified since it was obtained in a very low yield. When
compound 2 was heated to reflux in toluene after 1 h, its 1H NMR
spectra did not show the characteristic AA0XX0 pattern, indicating
the lost of the coordinated pyridine ligand.
Compound 2 was characterized by the usual spectroscopic
methods (Table 1). The 1H NMR spectrum of 2, obtained at r. t.,
shows signals corresponding to the phenyl rings and two signals in
the aromatic region as an AA0XX0 system due to the four pyridine
J
13Ce31
P
the red compound [Ru3(CO)10
yield, Scheme 1, a yellow compound identified, from the spectro-
scopic data, as [Ru3( -Cl)2(CO)8(PPh3)2] in 10% yield, this complex
must be a result of starting material decomposition, in agreement
(m-AuPPh3)(m-SC5H4N)] (2) in 69%
0
0
0
0
m
hydrogen atoms. This system displays JAA , JAX, JA X and JXX
couplings, which were determined using a simulation program

2180
M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
Fig 1. 13C{1H} NMR spectrums in the carbonyl region of compounds 1 (up) and 2 (down).
[23], and full assignment was made by comparison with previous
work in the field [21]. The signal at 8.31 ppm corresponds to the
THF for 1 h observing once again an insoluble solid and the same
behavior mentioned before. This behavior has been described
before for the reactions between [Ru3(CO)12] and bidentate amines
as well under refluxing THF [24e27], in which a solid insoluble
residue was obtained, probably of polymeric nature.
0
Hx and Hx diamagnetic deshielded hydrogen atoms, closer to the
nitrogen atom and the signal at 7.36 ppm correspond to the HA
and HA hydrogen atoms closer to the sulfur atom. The 31P{1H}
0
NMR spectrum obtained at room temperature shows a singlet at
73.0 ppm from the phosphine group, the signal shows a set of
To achieve the isolobal analog to compound 2, the protonation
reaction of [Ru3(CO)10(m-AuPPh3)(m-SC5H4N)] (2) was carried out
satellites by coupling with 13C due with a 1J
coupling of
using CF3CO2H (1:4) in CDCl3 at 25 ꢂC in an NMR tube and it was
13Ce31
P
45.1 Hz, the isotopomeric effect 1D13/12C value found was
ꢀ23.1 ppb. The 13C{1H} NMR spectrum of 2 obtained at room
temperature shows the expected carbon atoms, resembling
compound 1 (Fig. 1). The assignment of the AA0XX0 system carbon
atoms was made by a 2-D heteronuclear correlation experiment
(see Table 1 for full assignment).
monitored by 1H NMR. The reaction occurs, giving the formation of
the isolobal compound [Ru3(CO)10(m-H)(m-SC5H4N)] after 10 min.
The signals of the AA0XX0 system for the new compound were
observed at 8.04 and 8.56 ppm respectively. A low frequency
a single signal at ꢀ15.70 ppm confirmed the replacement of the
[AuPPh3]þ fragment by a Hþ to give a hydride ligand. The reaction
was monitored several hours and it was observed that the yield of
this compound was increased, but also other several species
On the other hand, several attempts to isolate the isolobal
analog to 2, compound [Ru3(CO)10(m-H)(m-SC5H4N)] were unsuc-
cessfully. The carried out experiments, involved the use of
[Ru3(CO)10(NCMe)2] as starting material, in the presence of 4-pyS
under different reaction conditions: i) ultrasonic bath “in situ” for
10 min, ii) stirring in dichloromethane at r. t. for 1 h or iii) refluxing
dichloromethane for 1 h; all tests gave as a result a yellow
precipitate. After evaporation to dryness, the residual solid could
not be redissolved and it was not further investigated. We also
carried out the reaction of [Ru3(CO)12] with 4-pyS in refluxing
were formed. Attempts to isolate the compound [Ru3(CO)10
(m-H)
(m-SC5H4N)] were unsuccessful. Therefore, we decided to prepare
a more stable derivative, containing a bidentate phosphine (dppe)
and test its reactivity with 4-pyS. It is important to achieve
a complex containing H- and S-ligands due to its possible appli-
cation in catalytic hydrogenation reactions and HDS processes [10].
The reaction between the known compound [Ru3(CO)10
(m-
dppe)] [28] with 4-pyS in THF for 1 h at 55 ꢂC gave compound

M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
2181
Scheme 2. Numbering sketch for compounds 3 and 4.
[Ru3(CO)8(
m
-H)(m
-SC5H4N)(m-dppe)] (3) selectively, in 50% yield
NMR spectrum of compound 4 was made by 2-D heteronuclear
(starting material was also recovered). It is remarkable that, when
the temperature rises above 55 ꢂC an orangeebrownish insoluble
solid appears.
correlation experiments and it is reported in Table 1 (see Scheme 2).
The protonation reaction of Ru3(CO)10
(m-AuPPh3)(m-SC5H4N)
(m
-dppe)] (4) was carried out using CF3CO2H (1:4) in CDCl3 at 25 ꢂC
The 31P{1H} NMR spectrum of 3, obtained at r. t., shows two
singlet signals belong to two different phosphorous atoms P1 and P2
in the phosphine group, with very similar chemical shifts. The 1H
NMR spectrum of 3, obtained at r. t., shows signals corresponding
to aromatic rings of the dppe and two other signals belong to the
AA0XX0 system of the pyridine ring. The full assignment of all
signals was accomplishes by using homo- and heteronuclear 2D
and selective irradiation experiments as well as long range bond
correlation (see Table 1 and Scheme 2). It is important to notice
that the 2D-NOESY NMR spectra of 3 shows a correlation between
in an NMR tube in order to determinate the formation of compound
Table 2
Selected bond lengths and angles for compounds 2and 3.
Bond lengths (Å)
Bond angles (ꢂ)
Compound 2
Ru(1)eS(1)
Ru(2)eS(1)
2.395(3)
2.403(3)
2.7650(9)
2.7641(9)
2.311(2)
2.836(1)
2.853(1)
2.892(1)
1.90(1)
1.89(1)
1.91(1)
1.89(1)
1.92(1)
Ru(2)eRu(1)eRu(3)
Ru(1)eRu(2)eRu(3)
Ru(1)eRu(3)eRu(2)
Ru(1)eS(1)eRu(2)
Ru(1)eAu(1)eRu(2)
C(11)eRu(1)eAu(1)
C(23)eRu(2)eAu(1)
C(12)eRu(1)eS(1)
C(22)eRu(2)eS(1)
Dihedral angles (ꢂ)
Ru(3)eRu(2)eRu(1)eAu(1)
S(1)eRu(1)eRu(2)eAu(1)
S(1)eRu(1)eRu(2)eRu(3)
59.74(3)
59.15(3)
61.11(3)
74.16(8)
63.08(3)
171.3(3)
167.2(4)
167.8(4)
168.5(4)
Au(1)eRu(1)
Au(1)eRu(2)
Au(1)eP(1)
Ru(1)eRu(3)
Ru(2)eRu(3)
Ru(1)eRu(2)
C(11)eRu(1)
C(12)eRu(1)
C(13)eRu(1)
C(21)eRu(2)
C(22)eRu(2)
C(23)eRu(2)
0
the signal belonging to the HAA protons of the pyridine ring and
those of phenyl ring 1Hmeta1 (see Scheme 2) revealing a close
interaction in solution between these two aromatic rings.
In order to synthesize the isolobal analog to 3, compound
[Ru3(CO)10(m-AuPPh3)(m-SC5H4N)(m-dppe)] (4), we carried out the
reaction of compound 3 with 1 equiv of [AuClPPh3] at r. t. for 1 h
using a base and a halide abstractor, KPF6, in CH2Cl2; the bases
used were NEt3 or n-BuLi or C10H8(NMe2)2, not observing conver-
sion to compound 4 in any case (see Scheme 1). We believe that
the replacement of the hydride by the [AuPPh3]þ fragment does
not take place due to steric hindrance.
127.93(3)
125.84(8)
106.23(8)
1.89(1)
Compound 3
Molecule 1
Ru(1)eS(1)
Ru(3)eS(1)
Ru(1)eRu(3)
Ru(1)eRu(2)
Ru(2)eRu(3)
Ru(1)eP(2)
2.4102(9)
2.402(1)
2.8674(5)
2.8666(4)
2.8316(4)
2.3114(8)
2.3434(8)
1.80(4)
Ru(2)eRu(1)eRu(3)
Ru(3)eRu(2)eRu(1)
Ru(2)eRu(3)eRu(1)
Ru(3)eS(1)eRu(1)
P(2)eRu(1)eRu(3)
P(3)eRu(2)eRu(3)
C(12)eRu(1)eS(1)
C(32)eRu(3)eS(1)
Dihedral angle (ꢂ)
59.18(1)
60.42(1)
60.394(9)
73.15(3)
139.40(2)
162.64(2)
165.5(1)
166.4(1)
An alternative approach was used to synthesize compound
[Ru3(CO)10(m-AuPPh3)(m-SC5H4N)(m-dppe)] (4); the reaction of 2
with dppe in dichloromethane at r. t. for 30 min gave compound 4,
in 25% yield, Scheme 1. Starting material was also recovered in
18.3% yield and several other products that we were not able to
identify and isolate due to their decomposition upon TLC purifica-
tion. When the reaction was carried out under refluxing CH2Cl2 for
1 h or by using CH3NO in CH2Cl2 at r. t. for 1 h, only traces of
compound 4 and decomposition products, mentioned before, were
observed.
Ru(2)eP(3)
Ru(1)eH(1)
Ru(3)eH(1)
C(7)eC(8)
C(7)eP(2)
C(8)eP(3)
C(12)eRu(1)
C(32)eRu(3)
Molecule 2
1.80(4)
1.532(4)
1.837(3)
1.844(3)
1.860(4)
1.893(4)
S(1)eRu(3)eRu(1)eRu(2)
P(3)eRu(2)eRu(1)eRu(3)
P(2)eRu(1)eRu(2)eRu(3)
104.48(3)
178.39(2)
144.26(2)
The 1H NMR spectrum of compound 4 obtained at room tem-
perature shows signals corresponding to the aromatic rings of the
dppe and two signals belonging to the AA0XX0 system of the pyri-
dine ring (see Table 1 and Scheme 2 for assignment). The 31P{1H}
NMR spectrum of 4 obtained at room temperature shows two
doublet resonances and one singlet signal; the double signal at
higher frequency (69.8 ppm) was assigned to the triphenylphos-
phinegold fragment (P3), and is coupled to the signal at 51.2 ppm
assigned to the phosphorous atom (P1) in the dppe diphosphine,
Ru(1A)eS(1A)
Ru(2A)eS(1A)
Ru(1A)eRu(2A)
Ru(1A)eRu(3A)
Ru(3A)eRu(2A)
Ru(1A)eP(2A)
Ru(3A)eP(3A)
Ru(1A)eH(1A)
Ru(2A)-H(1A)
C(7A)eC(8A)
C(7B)eP(2A)
C(8B)eP(3A)
C(11A)eRu(1A)
C(22A)eRu(2A)
2.4133(9)
2.4131(9)
2.8564(5)
2.8714(5)
2.8295(6)
2.3193(9)
2.348 (1)
1.82(4)
Ru(2A)eRu(1A)eRu(3A)
Ru(2A)-Ru(3A)eRu(1A)
Ru(3A)eRu(2A)-Ru(1A)
Ru(1A)e(1A)eRu(2A)
P(3A)eRu(1A)eRu(2A)
P(1A)eRu(3A)eRu(2A)
C(11A)eRu(1A)eS(1A)
C(22A)eRu(2A)eS(1A)
Dihedral angle (ꢂ)
59.21(1)
60.13(2)
60.66(1)
72.57(3)
140.14(2)
162.58(3)
164.8 (1)
167.7(1)
1.84(4)
with a 3J
P of 41.6 Hz trough the RueAu bond The singlet signal
31Ce31
1.533(5)
1.843(3)
1.845(4)
1.848(4)
1.917(4)
S(1A)eRu(1A)eRu(2A)eRu(3A)
P(2A)eRu(1A)eRu(3A)eRu(2A)
P(2A)eRu(1A)eRu(3A)eRu(2A)
105.49(4)
178.05(2)
145.47(2)
at 47.0 ppm corresponds to the phosphorous atom (P2) in the dppe
diphosphine; it shows a set of satellites by coupling with 13C with
a
1J
of 41.6 Hz, the isotopomeric effect 1D13/12C value found
P
13Ce31
was ꢀ44.1 ppb. The full assignment of all carbon atoms in the 13C

2182
M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
2.1.1. Compound 2
An ORTEP diagram of the structure of 2, Fig. 2, reveals the
“butterfly” arrangement of the metal atoms core, the dihedral angle
between the two planes [Au(1)eRu(1)eRu(3) and Ru(1)eRu(2)eRu
(3)] is 127.93(3)ꢂ. The gold atom is located in a wing-tip position of
the “butterfly”. Both the SC5H4N and the AuPPh3 fragments are
bridging the Ru(1)eRu(3) bond, being the longest RueRu distance
in the ruthenium triangle, 2.892(1) Å. The phosphine ligand is
terminally attached to the gold atom with a distance P(1)eAu(1) of
2.311(2) Å. The SC5H4N ligand bridges the Ru(1)eRu(3) bond trough
the sulfur atom, the body of the “butterfly”, and the angles formed
by S(1)eRu(1)eRu(3) and Ru(1)eRu(2)eRu(3) planes and S(1)eRu
(1)eRu(3) and Au(1)eRu(1)eRu(3) planes are 106.23(8)ꢂ and
125.84 (8)ꢂ respectively. The pyridine ring is pointing out of the
ruthenium atoms ring, with an angle between the planes defined
by the three ruthenium atoms and the pyridine ring of 86.8(4)ꢂ and
deviated approximately 3.2ꢂ from the perpendicular. The CO
ligands trans to the sulfur and gold bridging atoms are in pseudo-
axial positions according to their bond angles, (see Table 2).
In the crystal packing of 2; an intermolecular
pꢀstacking
interaction between two aromatic rings of the triphenylphosphine
fragment was observed, the type of contact found is a “face-to-face”
(parallel displacement) intermolecular aromatic interaction [29]
(see Fig. 3) and it has a ring centroide (Cg1)/H(54) of 3.42(8) Å,
C(54)&ctdotH(54) of 3.22(1) Å and C(54)/C(54) of 3.33(2) Å
non-bonding distances. This last distance is shorter than the sum of
van der Waals radii (SVwRCꢀC ¼ 3.4 Å) [30] and longer than the sum
of covalent radii (SCRCeC ¼ 1.46 Å) [31]. The distance found
between the centroides (Cg1)/(Cg2) of the two different rings was
4.800(9) Å, the interplanar distance between the two parallel rings
of 3.55(2) Å is closely related to the sum of the van der Waals radii
of two carbon atoms between two benzene molecules (3.4 Å) [32],
it was also found a distance (Cg1)/ring plane of 3.24(2) Å. This
stacking interaction probably contributes to the stabilization of
the crystal packing.
Fig. 2. ORTEP view of compound 2 (30% probability).
3, by exchange the isolobal [AuPPh3]þ fragment by a Hþ. The
reaction was monitored by 1H NMR for 24 h, after that time of
reaction there was no evidence of formation of compound 2, we
only observed the decomposition of the compound 4 to give
a mixture that it was not further analyzed.
2.1.2. Compound 3
2.1. X-ray diffraction studies
There are two molecules of 3 present in the asymmetric unit
having a C1 symmetry, the two crystallographically independent
molecules in the asymmetric unit are closely similar (Table 3). An
ORTEP diagram of one molecule is shown in Fig. 4, which confirms
the geometry suggested by the spectroscopic data. The structure
has a Cs symmetry and consists of a trigonal array of the metallic
Single crystal X-ray diffraction studies were carried out to
confirm the solid state structures of compounds 2 and 3. Some
selected bond lengths (Å) and bond and dihedral angles (ꢂ) are
collected in Table 2 for these compounds.
Fig. 3. Lateral view of compound 2 showing the phenyl ring interplanar distance in the structure.

M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
2183
Table 3
roughly located in the plane of the metal atoms accordingly with
the distance P(3)-Ruthenium plane of 0.065 Å for molecule 1 and
0.078 Å for molecule 2, with a dihedral angle P(3)eRu(2)eRu(1)e
Ru(3) of 178.39(2)ꢂ for molecule 1 and 178.05(2)ꢂ for molecule 2,
however the P(2) is located above the metal triangle approximately
1.337 and 1.304 Å for molecule 1 and 2 respectively, with a dihe-
dral angle P(2)-Ru(1)-Ru(2)-Ru(3) of 144.26(2)o and 145.47(2)o for
molecule 1 and 2 respectively. The RueP and RueC bond lengths
fall within normal values for ruthenium(0). Alike to compound 2, in
3 the CO ligands are located in trans positions to the sulfur atom in
a pseudo-axial orientation (see bond angles, Table 2).
The pyridine ring and the plane formed by the three ruthenium
atoms show interplanar angles of 82.1(1)ꢂ for molecule 1 and 87.1
(1)ꢂ for molecule 2, indicating that it is oriented similarly to the
one found in compound 2. The angle formed by the S(1)eRu(1)eRu
(3) and Ru(1)eRu(2)eRu(3) planes is 104.48(3)ꢂ for molecule 1 and
105.49(3)ꢂ for molecule 2.
Crystal data and structure refinement parameters for 2 and 3.
Compound
2
3
Empirical formula
Formula weight
Crystal color and shape
Crystal system
Crystal size (mm)
Space group
Unit cell dimensions
a (Å)
b (Å)
C33H19AuNO10PRu3S
1152.70
Red prism
C39H29NO8P2Ru3S
1036.84
Red block
Monoclinic
Triclinic
0.13 ꢃ 0.11 ꢃ 0.09
0.35 ꢃ 0.25 ꢃ 0.15
P21/c
Pꢀ1
9.25210(10)
12.0304(2)
33.8088(6)
90.00
97.6410(10)
90.00
3729.72(10)
4
2.053
16.20200(10)
17.83900(10)
19.8200(2)
92.044(11)
112.385(11)
116.694(11)
4581.8(8)
4
c (Å)
a
b
g
(ꢂ)
(ꢂ)
(ꢂ)
V, (Å3)
Z
Dcalcd, (Mg mꢀ3
)
1.59
1.226
m
, (mmꢀ1
)
5.266
In the structure, an intermolecular short contact between the
nitrogen atom of the 4-pyS of molecule 1 and the Hortho atom of one
phenyl ring bonded to P(3A) in the diphosphine ligand of molecule
2, was observed, fixing the aryl rings in solid state. The non-bonded
distances found, C(302A)/N(4) of 3.428(5) Å and H(3A2)/N(4) of
2.660(4) Å, are shorter than the sum of Van der Waals radius
(SVwRCeN ¼ 3.25 Å and SVwRNꢀH ¼ 2.75 Å) [30] and longer than the
sum of covalent radii’s (SCRCeN ¼ 1.44 Å and SCRNꢀH ¼ 1.02 Å) [31].
It is also worth noticing that a short non-bonding distance
was observed between H(6/6A)/C(203/209A) [3.134(6) for mole-
cule 1 and 3.563(4) for molecule 2]. Nonetheless, these distances
are longer than the sum of Van der Waals radii (SVwRCꢀH ¼ 2.9 Å)
[30], this possible interaction is in agreement with the correlation
observed in solution, in the 2D-NOESY NMR spectra, between the
Temperature (K)
(Mo-K ) (Å)
Scan type
range (ꢂ)
Index ranges
(hmin/hmax, kmin/kmax,
lmin/lmax)
293(2)
0.71073
293(2)
0.71073
ue4
6.28e54.98
l
a
u
e
4
2
q
5.84e57.42
ꢀ12/12, ꢀ16/16, ꢀ44/43 ꢀ20/20, ꢀ23/23, ꢀ25/25
Reflections collected
Independent reflections
Observed reflections
Parameters/restrains
Rfinal; Rall data
26309
82601
8918 (Rint ¼ 0.0657)
20551 (Rint ¼ 0.0392)
5013 (F > 4
s
(F))
15896 (F > 4s(F))
431/0
934/21
0.0657, 0.1402
0.1501, 0.1856
1.004
1.837/ꢀ1.761
0.0392, 0.0585
0.1108, 0.1308
0.941
0.58/ꢀ0.591
Rwfinal, Rwall dataa
GOF (all data)
Max, min peaks (eÅꢀ3
)
a
wꢀ1
¼
s
2(F2o) þ (P)2 þ P, where P ¼ (Fo2 þ 2F2c)/3.
0
HAA and Hmeta1 protons. This proximity might be able to prevent
free rotation of pyridine and phenyl rings in solid state.
atoms, with the sulfur atom of the SC5H4N ligand bridging the Ru
(1)eRu(3) bond. The hydride, which was observed in solution,
could not be located in the X-ray diffraction study, its position was
calculated and the results suggest that it also bridges the Ru(1)eRu
(3) bond, which is in agreement with the signal multiplicity
observed in the 1H NMR spectrum. The Ru(1)eRu(2) and Ru(1)eRu
(3) distances are longer than the Ru(2)eRu(3) distance, presumably
this is caused by the dppe and 4-pyS bridging ligands in these
bonds. The coordination fashion of the bidentate phosphine is the
3. Conclusions
The use of an activated ruthenium cluster as starting material for
the preparation of gold-substituted derivatives represents a great
advantage over the thermal activation route; in this manner we
were able to produce 1 in quantitative yield. In addition, the halide
can be easily substituted in the heteronuclear compound 1 by the
thiolato ligand to obtain compound [Ru3(CO)10
SC5H4N)] (2). We only observed the isolobal analog [Ru3(CO)10
-SC5H4N)] in solution by NMR spectroscopy, but it was not
possible to isolate it. The mixed rutheniumegold cluster
[Ru3(CO)10 -AuPPh3)( -SC5H4N)( -dppe)] (4) with thiolato and
phosphine ligands can only be obtained from compound 3. All the
experiments carried out with [Ru3(CO)10 -H)( -SC5H4N)( -dppe)]
(m-AuPPh3)(
m-
-H)
same than in the parent cluster [Ru3(CO)10(m-dppe)]. The P(3) is
(m
(m
(m
m
m
(m
m
m
(3) trying to prepare 4, its isolobal analog, were unsuccessful. It
is noteworthy that, throughout our experiments, no evidence
was obtained of N-coordination to the ruthenium atoms.
4. Experimental section
4.1. General procedures and materials
All reactions were carried out under nitrogen atmosphere.
Commercial TLC plates (silica gel 60 F254) were used to monitor
the progress of the reactions. All chemicals were supplied by
Aldrich Company except chloro(triphenylphosphine)gold(I) which
was supplied by Strem Chemicals, all reagents were used without
further purifications. Solvents were dried prior to use by standard
techniques and trimethylamine N-oxide dihydrate was sublimed
several times in high-vacuum to remove water. Compound
Fig. 4. ORTEP view of compound 3 (30% probability).
[Ru3(CO)10(m-dppe)] was prepared and purified according to the

2184
M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
method described before [28]. Infrared spectra for all compounds
were recorded as a solid thin film on a CsI window on a GX Per-
kineElmer 2000 FT-IR instrument. NMR spectra were obtained
using a JEOL Eclipse 400 spectrometer, with 1H and 13C spectra
relative to SiMe4, and 31P spectra relative to 85% aq. H3PO4. All
spectra were obtained in CDCl3. Elemental analyses were obtained
in a PerkineElmer series II Analyzer 2400. Mass spectra were
recorded at CINVESTAVeMéxico (HR-LC 1100/MSD TOF Agilent
Technology equipment).
4.5. Synthesis of compound [Ru3(CO)8(m-AuPPh3)(m-SC5H4N)(m-
dppe)] (4)
A mixture of [Ru3(CO)10(m-AuPPh3)(m-SC5H4N)] (2) (47 mg,
0.041 mmol) and dppe (16 mg, 0.041 mmol) in 10 mL of dichloro-
methane was stirred at r. t. for 30 min. The reaction mixture was
dried under vacuum and the solid residue was redissolved in
a minimal amount of chloroform and separated by TLC (eluent:
chloroformehexane (80:20 v/v)). The second red band obtained
afforded compound 2 (8.6 mg, 18%), the third band gave the dark
red compound [Ru3(CO)8(
m-AuPPh3)(m-SC5H4N)(m-dppe)] (4).
(15.3 mg, 25%) HR-MS (ESI-TOF); [MH]þ for (C57H43NO8P3SRu3Au)
4.2. Synthesis of compounds [Ru3(CO)10(m-Cl)(m-AuPPh3)] (1)
calcd 1497.8791, found 1497.8779. IR n(CO): 2037 (vs), 1999 (s),
1958 (vs, br), 1904 (m) cmꢀ1. The first and fourth bands were
not further characterized due to its unstable behavior during
purification process.
A solution of trimethylamine N-oxide dry, (CH3)3NO, (8.3 mg,
0.11 mmol) in acetonitrile (5 mL) was added dropwise to
a solution of [Ru3(CO)12] (30 mg, 0.047 mmol) in dichloro-
methane (18 mL) at ꢀ78 ꢂC, in a dry iceeacetone bath, over
a period of 15 min. After that period of time, the solution was
removed from the dry ice bath and it was slowly warmed to r. t.;
5. Crystallography
complete conversion of [Ru3(CO)12
] into [Ru3(CO)10(MeCN)2]
Suitable crystals of 2 and 3 were obtained by slow evaporation
of pentane:CHCl3 (1:3) and CHCl3 solutions respectively at low
temperature (5 ꢂC) for several days. Details for data collection
structure refinement for 2 and 3 are presented in Table 2. Data
were collected in an Enraf-Nonius Cappa CCD area detector
(31.2 mg, 0.047 mmol) had occurred after 15 min approximately
(TLC control). The compound [AuClPPh3] (23.3 mg, 0.047 mmol)
was then added “in situ” to the solution of [Ru3(CO)10(NCMe)2]
and stirred at r. t. for 1.5 h. The solvent was removed under
reduced pressure and the purple solid obtained was identified as
diffractometer using MoKa radiation. The samples were mounted
compound [Ru3(CO)10
C28H15O10ClPAuRu3 (1078.0235): HR-MS (ESI-TOF); [MeCleCO]þ
for (C27H15O9PRu3Au) calcd 1016.7244, found 1016.7239. IR
(CO): 2089 (s), 2075 (d), 2041 (vs), 2010 (vs), 1989 (sh), 1963
(m) cmꢀ1
(m-Cl)(m-AuPPh3)] (1), (50.7 mg 100%).
in MicroMounts (MiTeGen company) www.mitegen.com. For all
compounds, all non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were fixed at idealized refined positions. Data
collection, determination of unit Cell and integration of Frames of
all compounds were carried out using the suite Collect software
[33] and HKL Scalepack [34]. A semi-empirical absorption correc-
tion method (SADABS) [35] was applied in all cases. All structures
were resolved by direct methods, completed by subsequent
difference Fourier synthesis, and refined by full-matrix least-
squares procedures using the SHELXe97 package [35]. The hydride
ligand position in 3 was calculated using the Xhydex program [36]
All crystallographic programs were used under WINGX program
[37].
n
.
4.3. Synthesis of compound [Ru3(CO)10
(
m-AuPPh3)(m-SC5H4N)] (2)
To the solution of [Ru3(CO)10 -Cl)(m
(m
-AuPPh3)] (1) (50.7 mg,
0.047 mmol) was added “in situ” 4-mercaptopyridine (5.2 mg,
0.047 mmol) and placed in an ultrasonic bath for 10 min, the color
change from purple to red. The solvent was removed under reduced
pressure, and the resulting residue was redissolved in a minimal
amount of dichloromethane and separated on TLC (eluent: chlor-
oformehexane (70:30 v/v)). The first band, orange, was identified
Acknowledgements
as the known compound [Ru3(m-Cl)2(CO)8(PPh3)2] [14] (4.0 mg,
10%), the second band, red, corresponds to an unidentified
compound, and the third band gave the red compound
Financial support was provided by the projects Consejo Nacional
de Ciencia y Tecnología (CONACYT, Mexico, Grants No.: J110.362/
2007, CBe2008e106849, 025424 and 84453) and UAEHePAI
e24Be2006. Additionally, MGHC, MHS and BAOF thank CONACYT
for their scholarships.
[Ru3(CO)10
TOF); [MH]þ for (C33H19NO10PSRu3Au) calcd 1155.7336, found
1155.7349. IR (CO): 2086 (s), 2031 (vs), 2006 (vs), 1981 (s), 1963
(s) cmꢀ1
(m-AuPPh3)(m-SC5H4N)] (2) (22.6 mg, 69%). HR-MS (ESI-
n
.
Appendix A. Supplementary data
4.4. Synthesis of compound [Ru3(CO)8(m-H)(m-SC5H4N)
CCDC 790862 and 790863 contain the supplementary crystal-
lographic data for 2 and 3. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif.
(m-dppe)] (3)
[Ru3(CO)10
(m-dppe)] was prepared according to the procedure
publish before [28]. A mixture of [Ru3(CO)10(m
-dppe)] (30 mg,
0.031 mmol) and 4-mercaptopyridine (3.4 mg, 0.031 mmol) in
15 mL of THF was heated to 55 ꢂC for 1 h. The solvent was then
evaporated under vacuum and the residue was separated by TLC
(eluent: CH2Cl2ehexane 80/20 v:v). The first orange band was
Appendix. Supporting information
Supporting information associated with this article can be fo-
und,in the online version, at doi:10.1016/j.jorganchem.2010.11.034.
identified as unreacted [Ru3(CO)10
second, deep orange band, was assigned to compound [Ru3(CO)8(
H)( -SC5H4N)(
-dppe)] (3) (15.8 mg, 50%). HR-MS (ESI-TOF); [MH]þ
(m-dppe)] (14 mg, 50%). The
m-
References
m
m
[1] P. Braunstein, L.A. Oro, P.R. Raithby (Eds.), Metal Clusters in Chemistry. Metal
Clusters as Model for Hydrodesulfurization Catalysts, Wiley-VCH, Germany,
1999 p. 605e615, 741e781 and references therein.
[2] R.D. Adams, E. Trufan, Phil. Trans. Royal Soc. 368 (2010) 1473e1493.
[3] Y. Li, W.-T. Wong, Eur. J. Inorg. Chem. (2003) 2651.
for (C39H30NO8P2SRu3) calcd 1039.8292, found 1039.8296. Anal. for
C39H29NO8P2SRu3 (Mw ¼ 1036.86): Calcd.: C, 45.18; H, 2.82; N, 1.35
Expt.: C, 45.62; H, 2.95; N, 1.34. IR n(CO): 2063 (vs), 2021 (s), 1990
(vs, br), 1952 (s), 1930 (sh) cmꢀ1
.

M.G. HernándezeCruz et al. / Journal of Organometallic Chemistry 696 (2011) 2177e2185
2185
[4] J. Evans, G. Jingxing, J. Chem. Soc. Chem. Commun. (1985) 39e40.
[5] E. LozanoeDiz, A. Neels, H. StoecklieEvans, G. SüsseFink, Polyhedron 20
(2001) 2771e2780.
[6] P. Homanen, R. Persson, M. Haukka, T.A. Pakkanen, E. Nordlander, Organo-
metallics 19 (2000) 5568e5574.
[7] P. Frediani, A. Salvini, S. Finocchiaro, J. Organomet. Chem. 584 (1999)
265e273.
[8] A. Chehata, A. Oviedo, A. Arévalo, S. Bernès, J.J. García, Organometallics 22
(2003) 1585e1587.
[20] T. Adatia, M. McPartlin, I.D. Salter, J. Chem. Soc. Dalton Trans. (1988) 751e765.
[21] G. SánchezeCabrera, F.J. ZunoeCruz, B.A. OrdóñezeFlores, M.J. RosaleseHoz,
M.A. Leyva, J. Organomet. Chem. 692 (2007) 2138e2147.
[22] S. Kerschl, A. Sebald, B. Wrackmeyer, Magn. Reson. Chem. 23 (1985) 514e520.
[23] H.M. Bell, FTNMR Simulation. Chemistry Department, Virginia Tech., Blacks-
burg, VA, 2003.
[24] J.A. Cabeza, I. da Silva, I. del Río, S. García-Granda, V. Riera,
M.G. SánchezeVega, Organometallics 22 (2003) 1519e1525.
[25] J.A. Cabeza, M.A. MartínezeGarcía, V. Riera, S. GarcíaeGranda, J.F. Van der
Maelen, J. Organomet. Chem. 514 (1996) 197e202.
[9] J.A. de los Reyes, Appl. Catal. A Gen. 322 (2007) 106e112.
[10] M. Shibue, M. Hirotsu, T. Nishioka, I. Kinoshita, Organometallics 27 (2008)
4475e4483.
[26] J.A. Cabeza, V. Riera, M. Angela Pellinghelli, A. Tiripicchio, J. Organomet. Chem.
376 (1989) C23eC25.
[11] I.D. Salter, in: F.G.A. Stone, R. West (Eds.). Adv. in Organomet. Chem.vol. 29,
Academic Press Inc., London, 1989, p. 249 (and references therein).
[12] I.D. Salter, in: G. Wilkinson, F.G.A. Stone, E.W. Abel (Eds.), Comprehensive
Organometallic Chemistry II, vol. 10, Pergamon Press., Oxford, 1995, p. 255
(and references therein).
[27] J.A. Cabeza, J.M. FernándezeColinas, V. Riera, M. Angela Pellinghelli,
A. Tiripicchio, J. Chem. Soc. Dalton Trans. (1991) 371e377.
[28] M.I. Bruce, T.W. Hambley, B.K. Nicholson, M.R. Snow, J. Organomet. Chem. 235
(1982) 83e91.
[29] W.B. Jennings, B.M. Farrell, J.F. Malone, Acc. Chem. Res. 34 (2001) 885e894.
[30] A. Bondi, J. Phys. Chem. 68 (1964) 441e451.
[31] B. Cordero, V. Gómez, A.E. Platero-Prats, M. Revés, J. Echeverría, E. Cremades,
F. Barragán, S. Alvarez, Dalton Trans. (2008) 2832e2838.
[32] E.V. GarcíaeBáez, F.J. MartínezeMartínez, H. Höpfl, I.I. PadillaeMartínez,
Cryst. Growth Des. 3 (2003) 35e45.
[33] Nonius, COLLECT. Nonius BV, Delft, The Netherlands, 2001.
[34] Z. Otwinowski, W. Minor, Methods in Enzymology. Academic Press, , New
York, 1997, p. 307.
[13] B.F.G. Johnson, J. Lewis, J.N. Nicholls, J. Puga, K.H. Whitmire, J. Chem. Soc.
Dalton Trans. (1983) 787e797.
[14] G. Lavigne, F. Papageorgiou, J.-J. Bonnet, Inorg. Chem. 23 (1984) 609e613.
[15] A.J. Deeming, K.I. Hardcastle, M. Karim, Inorg. Chem. 31 (1992) 4792e4796.
[16] S. Jeannin, Y. Jeannin, G. Lavigne, Inorg. Chem. 17 (1978) 2103e2110.
[17] J.A. Cabeza, I. Del Río, P. GarcíaeÁlvarez, D. Miguel, J. Organomet. Chem. 692
(2007) 3583e3587.
[18] E. Delgado, E. Hernández, M.A. Maestro, A. Nievas, M. Villa, J. Organomet.
Chem. 691 (2006) 3596e3601.
[19] S.S.D. Brown, S. Hudson, I.D. Salter, M. McPartlin, J. Chem. Soc. Dalton Trans.
(1987) 1967e1975.
[35] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112e122.
[36] A.G. Orpen, J. Chem. Soc. Dalton Trans. (1980) 2509e2516.
[37] L.J. Farrugia, J. Appl. Cryst. 32 (1999) 837e838.