Sulfido-carbonyl ruthenium clusters derived from tertiary phosphine sulfides

Article abstract of DOI:10.1016/S0020-1693(02)01455-X

The reactions of Ru₃(CO)₁₂ with 2,4,6 tris-(trimethoxy)phenylphosphino sulfide (ttmppS) and with 1,2 bis-[(diphenylphosphino)methyl]benzene disulfide (dpmbS₂) afford a variety of phosphine substituted sulfido carbonyl clusters. These belong to three different families of clusters showing, respectively, (i) the Ru₃S (compound 4), (ii) the Ru₃S₂ (compound 3), and (iii) the Ru₄S₂ cores (compounds 1 and 2). Similar distributions of products have been observed in the case of the reactions between M₃(CO)₁₂ (M=Ru or Fe) and phosphine and diphosphine selenides. The structures of complexes 1-4 have been determined by X-ray diffraction methods.

Full text of DOI:10.1016/S0020-1693(02)01455-X

Inorganica Chimica Acta 347 (2003) 137Á144
/
www.elsevier.com/locate/ica
SulfidoÁ
/
carbonyl ruthenium clusters derived from tertiary phosphine
sulfides
Daniele Belletti, Claudia Graiff, Virginia Lostao, Roberto Pattacini, Giovanni Predieri,
Antonio Tiripicchio *
Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universita` di Parma, Parco Area delle Scienze 17/A, I-43100
Parma, Italy
Received 15 May 2002; accepted 24 July 2002
Dedicated to the extraordinary and long career of Professor Rafael Uso´n, which has accompanied all the growth of Spanish Organometallic
Chemistry
Abstract
The reactions of Ru3(CO)12 with 2,4,6 tris-(trimethoxy)phenylphosphino sulfide (ttmppS) and with 1,2 bis-[(diphenylphos-
phino)methyl]benzene disulfide (dpmbS2) afford a variety of phosphine substituted sulfido carbonyl clusters. These belong to three
different families of clusters showing, respectively, (i) the Ru3S (compound 4), (ii) the Ru3S2 (compound 3), and (iii) the Ru4S2 cores
(compounds 1 and 2). Similar distributions of products have been observed in the case of the reactions between M3(CO)12 (Mꢀ
/
Ru
or Fe) and phosphine and diphosphine selenides. The structures of complexes 1Á4 have been determined by X-ray diffraction
/
methods.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Sulfido complexes; Ruthenium complexes; Crystal structures; Cluster complexes
1. Introduction
reactions take advantage of the frailty of the PÄ
/
Se bond
and provide a simple, sometimes selective [8] synthetic
route to phosphine-substituted, mono- and diselenido
trinuclear clusters. Further pyrolytic processes usually
lead to the formation of tetrahedral species M2Se2, in
the case of iron, and octahedral species M4Se2, in the
case of ruthenium (see Scheme 1). Occasionally, other
less common compounds can be obtained via condensa-
tion processes such as clusters containing butterfly
M6Se4 cores [9] (represented in Scheme 1) and the
cubane-like cage complex [Ru4(m3-Se)4(CO)10(m-dppm)]
[10].
The chemistry of transition-metal sulfido, selenido
and tellurido mono- and polynuclear complexes is a
research area of increasing interest, as pointed out in
recent reviews [1Á3]. The reasons for this growing
/
interest derive from the usefulness of these ligands in
cluster growth reactions and from the search for
precursors of nanoparticles with novel electronic, mag-
netic and optical properties [3,4], considering the size-
dependence of physico-chemical properties of sub-
stances such as metals and semiconductors [5,6].
In recent years we have carried out systematic
investigations on the selenium transfer reactions by
tertiary phosphine and diphosphine selenides, namely
Ph3PSe, (tppSe), CH2(Ph2PSe)2, (dppmSe2), (CH2Ph2-
PSe)2, (dppeSe2), Fe(h5-C5H4Ph2PSe)2, (dppfcSe2), to-
wards iron and ruthenium carbonyl clusters [7]. These
Continuing these investigations, we have recently
observed that tertiary phosphine selenides bearing
heterocyclic fragments, such as 2-thienyl (th), 2-pyridyl
(py) and 5-(2-pyridyl)-2-thienyl (pyth), can undergo PÁ
/
C bond cleavage by reaction with iron and ruthenium
carbonyl clusters. Actually in the case of Ph2(th)PSe and
Ph2(py)PSe with ruthenium, the addition is not only
limited to the transfer of the chalcogenido atom, but
* Corresponding author. Fax: ꢁ
/
39-0521-905-557.
E-mail address: tiri@unipr.it (A. Tiripicchio).
proceeds with PÁ
/
C bond cleavage, affording selenidoÁ
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01455-X

138
D. Belletti et al. / Inorganica Chimica Acta 347 (2003) 137Á144
/
Scheme 1.
phosphido clusters [11,12]. In particular in the case of
the thienyl group, the 48-electron cluster [Ru3(m3-Se)(m-
PPh2)(m-th)(CO)6{P(th)Ph2}] has been obtained in good
yields by a one step synthesis. Its molecular structure
shows the contemporary presence of the diphenylphos-
phido (bridging one side) and selenido (capping) ligands
on the same cluster core [13].
in the synthesis of Pd, [21,22] Pt, [23Á25] Ni, [25] and Ag
/
[26] complexes, where the diphosphine acts mostly as a
chelating ligand bearing to the formation of stable seven
membered chelating rings, whose conformations have
been studied in solid state as well as in solution.
Finally we have reacted different phosphine selenides
Fe or
2. Experimental
with the tetrahedral clusters [HMCo3(CO)12] (Mꢀ
/
Ru) in order to obtain new chalcogenidoÁcarbonyl
/
bimetallic clusters [14] considering that the presence of
different metals can influence the selectivity of certain
processes [15,16] and lead to the formation of com-
pounds presenting new and not always easily predictable
structures.
2.1. General
The starting reagents Ru3(CO)12, sulfur and tertiary
phosphines were pure commercial products (Aldrich
and Fluka) and were used as received. The solvents (C.
Erba) were dried and distilled by standard techniques
before use. All manipulations (prior to the TLC separa-
tions) were carried out under dry nitrogen by means of
standard Schlenk-tube techniques. Elemental (C, H, S)
analyses were performed with a Carlo Erba EA 1108
automated analyzer. IR spectra (KBr discs or CH2Cl2
solutions) were recorded on a Nicolet 5PC FT or a
Nicolet Nexus FT spectrometer. 1H (300 MHz), 31P
(81.0 MHz, 85% H3PO4 as external reference) NMR
spectra (CDCl3 solutions) were recorded on Bruker
instruments AC 300 (1H) and CXP 200 (31P).
Mass spectra were obtained using a Finnigan MAT
SSQ710 spectrometer equipped with an IC/CI source, a
direct inlet system and a quadrupole mass analyzer was
used. The CI source was utilized with methane as the
reagent gas (T source, 220 8C; methane ionization
energy, 70 eV). The quadrupole temperature was main-
tained at 140 8C; the system was scanned from 400 to
1600 a.m.u. and negative ion (NICI) spectra were
recorded.
As a natural extension of these investigations, we have
decided to react carbonyl metal clusters such as
M3(CO)12 (MꢀFe or Ru) with tertiary phosphine
/
sulfides with the aim to observe the transfer of sulfur
atoms to zero-valent metal complexes leading to sulfido
carbonyl ruthenium clusters substituted by tertiary
phosphines. Previous investigations on the reactions of
phosphine sulfides with carbonyl complexes involved
Ph3PS [17], Ph2P(S)H [18], {PhP(S)}2CH2 and
PhP(S)CÅ/CR [19].
This paper deals with the reactions between
Ru3(CO)12 and mono- and diphosphine sulfides such
as 2,4,6 tris-(trimethoxy)phenylphosphino sulfide
(ttmppS) and 1,2 bis-[(diphenylphosphino)methyl] ben-
zene disulfide (dpmbS2) and with the characterization of
the derived sulfidoÁcarbonyl ruthenium clusters. As
/
regards the dpmb diphosphine, even if its preparation
has been reported several years ago [20], nevertheless its
coordination chemistry appears to have been little
investigated. In particular it has been utilized as ligand

D. Belletti et al. / Inorganica Chimica Acta 347 (2003) 137Á
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139
2.2. Preparation and reactions
hexane 1:1) yielded a orange band, a yellow one, a red
one and two deep red bands together with some
decomposition. The red band and the two deep red
bands contained, respectively, the closo cluster [Ru4(m4-
S)2(CO)8(m-CO)(m-dpmb)] (2, yield 15%), the nido
cluster [Ru3(m3-S)2(CO)7(dpmb)] (3, yield 30%) and the
monosulfido cluster [Ru3(m3-S){m-P(Ph)CH2C6H4-
CH2PPh2}(m-OCPh)(CO)6] (4, yield 2%), whose struc-
tures have been determined by spectroscopic and X-ray
diffraction methods.
2.2.1. Preparation of the phosphine sulfides
The ligands ttmppS and dpmbS2 were prepared by
elemental sulfur transfer.
A toluene suspension (20 ml) of elemental sulfur (30
mg, 0.94 mmol) was added to a solution of 500 mg (0.94
mmol) of ttmpp in 25 ml of toluene. The mixture was
refluxed for 5 h. The solvent was removed in vacuo and
the rough powder was used as obtained. Yield 85%.
Anal. Found: C, 57.41; H, 5.85; S, 5.62. C27H33O9PS
Cluster 2: IR (CH2Cl2, nCO, cmꢂ1): 2048s, 2017vs,
Calc.: C, 57.44; H, 5.89; S, 5.68%. FTIR (KBr) (cmꢂ1):
1999vs, 1974s, 1824w. H NMR (CHCl3-d1): 7.61Á
/6.89
1
1
682 s, 660 vs (nPÄ
/
S). H NMR (CHCl3-d1): d 6.03 (d,
(m, 20Har), 6.20Á5.59 (m, 4Har), 3.75 (m, 4H, CH2).
/
2J(H,P) 4Hz, 6Har), 3.77 (s, 9H, p-Me), 3.53 (s, 18H, o-
Me). 31P NMR (CHCl3-d1): 11.3 (s). MS NICI, m/z
(%):564 (ttmppS)ꢂ (100); 532 (ttmp)ꢂ, (15); 365 (2,4,6
tris OCH3-C6H2)2P)ꢂ, (40).
Anal. Found: C, 41.25; H, 2.45; S, 5.42. Ru4S2-
P2O9C41H28 Calc.: C, 41.20; H, 2.36; S, 5.36%.
Cluster 3: IR (CH2Cl2, nCO, cmꢂ1): 2074vs, 2041vs,
1
1999sh, 1995s, 1946w. H NMR (CHCl3-d1): 7.93Á
/6.66
20 ml of a toluene suspension of elemental sulfur (67
mg, 2.10 mmol) was added to a solution of 500 mg (1.05
mmol) of dpmb. The mixture was refluxed for 6 h. The
solvent was removed and the rough powder was used as
obtained. Yield 87%. Anal. Found: C, 71.41; H, 5.21; S,
(m, 20Har), 6.23 (m, 2Har), 5.87 (m, 2Har), 4.37 (m, 2H,
CH2) 3.85 (m, 2H, CH2). Anal. Found: C, 45.41; H,
2.85; S, 6.12. Ru3S2P2O7C39H28 Calc.: C, 45.13; H, 2.72;
S, 6.18%.
Cluster 4: IR (CH2Cl2, nCO, cmꢂ1): 2038m, 2020vs,
1993s, 1968sh. 31P NMR (CHCl3-d1): 218.2 (s), 33.2 (s).
Anal. Found: C, 46.01; H, 2.86; S, 3.14. Ru3S-
P2O7C39H28 Calc.: C, 46.58; H, 2.80; S, 3.19%.
11.81. C32H28P2S2 Calc.: C, 71.36; H, 5.24; S, 11.90%.
FTIR (KBr) (cmꢂ1): 602 vs (nPÄ
1
S). H NMR (CHCl3-
/
d1): d 7.81Á
/
7.32 (m, 20H, Ph), 6.86 (m, 2Har), 6.55 (m,
2Har), 3.99 (d, 2J(H,P) 11Hz, 4H). 31P NMR (CHCl3-d1):
39.1 (s). MSÁ
/
NICI, m/z (%): 538 (dpmbS2)ꢂ (70); 321
2.3. X-ray data collection, structure solution and
(PCH2(C6H4)CH2PPh2)ꢂ, (100); 217 (Ph2PS)ꢂ, (40).
refinement for complexes 1×
/
0.5CHCl3, 2×
/
0.5CH2Cl2, 3
and 4
2.2.2. Reaction of ttmppS with Ru3(CO)12
Ru3(CO)12 (300 mg, 0.47 mmol) and ttmppS (264 mg,
0.47 mmol, 1:1 molar ratio) were reacted in hot toluene
(100 ml) at 50 8C for about 1.5 h, in the presence of
Me3NO (35 mg), under nitrogen atmosphere. The deep
red solution was evaporated to dryness and the residue
was disolved in a small amount of CH2Cl2. Preparative
TLC (Kieselgel P.F. Merck, eluant mixture tetrahydro-
furan/toluene 2:1) yielded a red band together with other
unresolved bands and some decomposition. The red
band contained the closo cluster [Ru4(m4-S)2(CO)8(m-
CO)2P{(2,4,6 OCH3)3(C6H2)}3] (1, yield 20%), identified
by X-ray diffraction methods.
The intensity data were collected at room temperature
on a Bruker AXS Smart 1000 diffractometer, equipped
with an area detector using a graphite monochromated
Mo Ka radiation. The SMART program package was
used to determine the unit-cell parameters and for data
collection. Crystallographic and experimental details for
structures are summarized in Table 1.
The poor quality of the crystals of cluster 4 prevented
accurate results of the structure determination. The
structures were solved by Patterson and Fourier meth-
ods and refined by full-matrix least-squares procedures
(based on Fo2) [27Á
30] with anisotropic thermal para-
/
Cluster 1: IR (CH2Cl2, nCO, cmꢂ1): 2060s, 2020vs,
meters in the last cycles of refinement for all the non-
hydrogen atom excepting for the carbon and chlorine
atoms of the solvent molecules in 1 and 2 and the carbon
and oxygen atoms of the molecule in compound 4. In
the crystals of 1 and 2 molecules of CHCl3 and CH2Cl2,
respectively, were found with occupancy factor 0.5.
In the structures the hydrogen atoms were introduced
into the geometrically calculated positions and refined
riding on the corresponding parent atoms, excepting for
those of the solvents. In the final cycles of refinement a
1
1984m, 1869w, 1828w. H NMR (CHCl3-d1): 5.89 (d,
2J(H,P) 4Hz, 6Har), 3.76 (s, 9H, p-Me), 3.58 (s, 18H, o-
Me). Anal. Found: C, 35.11; H, 2.62; S, 5.02. Ru4S2-
PO19C37H33 Calc.: C, 34.69; H, 2.59; S, 5.00%.
2.2.3. Reaction of dpmbS2 with Ru3(CO)12
Ru3(CO)12 (300 mg, 0.47 mmol) and dpmbS2 (252 mg,
0.47 mmol, 1:1 molar ratio) were reacted in hot toluene
(100 ml) at 70 8C for about 3 h, in the presence of
Me3NO (35 mg), under nitrogen atmosphere. The deep
red solution was evaporated to dryness and the residue
was dissolved in a small amount of CH2Cl2. Preparative
TLC (Kieselgel P.F. Merck, eluant mixture CH2Cl2/
weighting scheme wꢀ
[s2Fo2ꢁ(0.0487P)2] (2), wꢀ
and wꢀ
1/[s2Fo2ꢁ(0.0001P)2ꢁ
Pꢀ
(Fo2ꢁ2Fc2)/3, was used.
/
1/[s2Fo2ꢁ
1/[s2Fo2ꢁ
179.9571] (4), where
/
(0.1363P)] (1), wꢀ
/
1/
/
/
/
(0.0273P)2] (3)
/
/
/
/
/

140
D. Belletti et al. / Inorganica Chimica Acta 347 (2003) 137Á
/144
Table 1
Crystal data and structure refinement for compound 1×
/
0.5CHCl3, 2×/0.5CH2Cl2, 3, 4
Compound
Formula
1×
/
0.5CHCl3
2×0.5CH2Cl2
Ru4S2P2O9C41H28
1237.44
/
3
4
Ru4S2PO19C37H33
1340.69
×
/
1/2CHCl3
×
/
1/2CH2Cl2
Ru3S2P2O7C39H28
1037.88
Ru3SP2O7C39H28
1005.82
Formula weight
Crystal system
Space group
monoclinic
C2/c
monoclinic
P21/n
monoclinic
P21/c
triclinic
¯
P1
Unit cell dimensions
˚
a (A)
˚
20.214(4)
18.005(4)
29.628(4)
90
14.157(4)
19.412(4)
16.348(4)
90
11.383(4)
18.872(5)
18.973(3)
90
10.135 (4)
11.219(3)
17.818(5)
98.82(5)
92.27(3)
93.10(5)
1997(1)
2
b (A)
˚
c (A)
a (8)
b (8)
g (8)
V (A )
Z
103.73(3)
90
100.85(3)
90
102.13(3)
90
3
˚
10475(3)
8
1.700
4412(2)
4
1.863
3985(2)
4
1.730
Dcalc (Mg mꢂ3
)
1.673
12.99
992
Absortion coefficient (cmꢂ1
F(000)
)
13.84
5272
16.24
2420
13.55
2048
Crystal size (mm3)
0.18ꢃ
1.42Á27.02
56876
/0.32ꢃ
/
0.37
0.22ꢃ
1.65Á27.01
26338
/0.13ꢃ
/
0.22
0.14ꢃ
1.54Á27.02
23881
/0.20ꢃ
/0.19
0.11ꢃ
1.84Á23.32
4485
/0.25ꢃ0.25
/
u Range (8)
Reflections collected
Independent reflections
/
/
/
/
11408 [Rint
7137
ꢀ
/
0.0599]
9526 [Rint
5228
ꢀ/
0.0508]
8618 [Rint
3966
ꢀ/
0.0708] 3929 [Rint
1893
ꢀ0.0339]
/
Observed reflections [I ꢀ
/
2s(I)]
Data/restr./param.
Goodness-of-fit on F2
11408/0/588
1.021
9526/0/541
0.918
8618/0/485
0.797
3929/0/245
1.067
Final R indices [I ꢀ
/
2s(I)]
R1ꢀ
wR2ꢀ
R1ꢀ0.0967,
wR2ꢀ0.2159
2.283 and ꢂ0.795
/
0.0537,
R1ꢀ
wR2ꢀ
R1ꢀ0.0981,
wR2ꢀ0.1089
0.645 and ꢂ0.696
/
0.0393,
R1ꢀ
wR2ꢀ
R1ꢀ0.1239,
wR2ꢀ0.0849
0.690 and ꢂ0.551
/
0.0409,
R1ꢀ
wR2ꢀ
R1ꢀ0.2386,
wR2ꢀ0.3024
1.207 and ꢂ1.194
/
0.1073,
/
0.1903
/0.0927
/
0.0692
/
0.2131
R indices (all data)
/
/
/
/
/
/
/
/
Largest difference peak and hole
ꢂ3
/
/
/
/
˚
(e A
)
R1ꢀ
/
ajjFojꢂ
/
jFcjj/ajFoj. wR2ꢀ
/
[a[w(Fc2ꢂ
/
Fo2)2]/a[w(Fo2)2]]1/2
.
All calculations were carried out on Digital AlphaS-
tation 255 computers.
and selenium/iron carbonyl compounds [7,8]. Cluster 3
could be described as a square pyramid with two metal
and two sulfur atoms alternating in the basal plane and
the third metal atom at the apex of the pyramid. The
dpmb chelates one of the ruthenium atoms at the base of
the pyramid.
3. Results and discussion
On the other hand, clusters 1 and 2 belong to the
family of Ru4S2 62 electron closo clusters with seven
skeletal electron pairs (structure III of Scheme 1). 1 is
the unique product isolable from the reaction between
dpmbS2 and Ru3(CO)12.
Clusters 1, 2 and 3 are substituted sulfido metal
carbonyl clusters, in which sulfur atoms are transferred
to the metal core and one or two carbonyl groups are
substituted by a mono or a diphosphine. It is interesting
to note that in this kind of reactions, carried out at
70 8C, the pyrolytic fragmentation of the dpmb occurs
3.1. Synthesis and spectroscopic characterization of the
compounds
The reactions of Ru3(CO)12 with different phosphine
sulfides, in hot toluene and in the presence of Me3NO as
decarbonylating agent, produce a variety of phosphine-
substituted sulfidoÁcarbonyl clusters, whose structural
/
frameworks are analogous to those found for phos-
phine-substituted selenido carbonyl clusters [7]. They
are air stable, colored solids and have been isolated by
TLC on silica gel [31] and characterized by spectroscopic
data. In some cases their slow crystallization allows to
obtain single crystals suitable for X-ray diffraction
analysis. In particular we obtained workable amounts
of cluster 3 (structure II of Scheme 1) showing a Ru3S2
core. This cluster belongs to the family of 50-electron
nido clusters with seven skeletal electron pairs; these
clusters are usually the main products of this kind of
reactions as observed in the case of selenium/ruthenium,
leading to the rupture of a PÁC(Ph) bond with release of
/
a phenyl group. This undergo CO migratory insertion
affording a benzoyl fragment bridging two Ru atoms as
reported in the description of the crystal structure (see
below). The same behaviour has been observed in the
case of the reaction between Ru3(CO)12 and the
dppfcSe2, where, among the minor products present in
the reaction mixtures, it was possible to isolate few

D. Belletti et al. / Inorganica Chimica Acta 347 (2003) 137Á
/144
141
crystals of the red derivative of formula [Ru3(m3-Se){m-
P(Ph)C5H4FeC5H4PPh2}(m-OCPh)(CO)6] [32]. This
cluster and compound 4 are very similar as they consist
of a trinuclear cluster with a Ru3E core (EꢀSe or S).
/
The chalcogenido atom caps the metal triangle, two
sides of which are bridged by a phosphido and a benzoyl
group.
3.2. Crystal structure determination of 1×
/
0.5CHCl3, 2×
/
0.5 CH2Cl2, 3 and 4
Views of the structures of 1 and 2 are shown in Figs. 1
and 2 together with atomic numbering scheme; selected
bond distances and angles are given in Tables 2 and 3.
Complexes 1 and 2 exhibit a distorted closo-octahe-
dral Ru4S2 core with seven skeletal electron pairs. In 1
Fig. 2. View of the molecular structure of cluster 2 with the atomic
labelling scheme. The thermal ellipsoids are drawn at the 30%
probability level.
two carbonyls asymmetrically bridge two adjacent RuÁ
/
Ru edges, which are the shortest of the four RuÁRu
/
˚
Ru3 and Ru3ÁRu4 2.749(1), 2.748(1) A,
respectively) as observed in many chalcogenido metal
clusters containing bridging carbonyl groups [7,33,34].
All the ruthenium atoms are also bound to two terminal
edges (Ru2Á
/
/
Table 2
List of bond lengths (A) and bond angles (8) for 1×
˚
/
0.5CHCl3
Bond lengths
Ru(1)Á
Ru(1)Á
Ru(2)Á
Ru(3)Á
Ru(1)Á
Ru(1)Á
Ru(2)Á
Ru(2)Á
Ru(3)Á
Ru(3)Á
/
Ru(2)
Ru(4)
Ru(3)
Ru(4)
S(1)
2.802(1)
2.819(1)
2.749(1)
2.748(1)
2.480(2)
2.508(2)
2.452(2)
2.473(2)
2.520(2)
2.527(2)
Ru(4)Á
Ru(4)Á
Ru(1)Á
Ru(3)Á
Ru(4)Á
Ru(3)Á
Ru(2)Á
/
S(1)
S(2)
P(1)
C(1)
C(1)
C(2)
C(2)
2.464(2)
2.481(2)
2.401(2)
carbonyls, whereas the phosphine ligand is bound to the
˚
Ru1 atom. The Ru1ÁP1 bond length, 2.401(2) A, is
/
/
/
/
/
/
/
2.139(11)
2.006(10)
2.299(11)
1.984(10)
1.166(12)
1.157(11)
slightly longer of that found in the analogous selenium
cluster [Ru4(m4-Se)2(CO)8(m-CO)2P(C6H5)3] [2.329(7)
and 2.338(7) A, respectively, for the two independent
/
/
/S(2)
/
˚
/S(1)
/
molecules] [34]. The RuÁS bond lengths span from
/
/S(2)
O(1)Á
/
C(1)
C(2)
˚
/S(1)
O(2)Á
/
2.452(2) to 2.527(2) A, while the Sꢀ ꢀ ꢀS separation is of
/S(2)
˚
3.050(3) A, in good agreement with the averaged values
˚
found in the Ru4S2 clusters (3.08 A) [7].
Bond angles
Ru(2)ÁRu(1)Á
Ru(3)ÁRu(2)Á
Ru(4)ÁRu(3)Á
Ru(3)ÁRu(4)Á
P(1)ÁRu(1)Á
P(1)ÁRu(1)Á
S(1)ÁRu(1)Á
S(1)ÁRu(2)Á
/
/
Ru(4)
Ru(1)
Ru(2)
Ru(1)
87.22(3) S(1)Á
91.71(3) S(1)Á
89.71(3) Ru(2)Á
91.36(3) Ru(1)Á
166.46(7) Ru(2)Á
95.80(7) Ru(1)Á
75.39(7) Ru(4)Á
76.53(7) Ru(2)Á
/
Ru(3)Á
Ru(4)Á
S(1)Á
S(1)Á
S(2)Á
S(2)Á
C(1)Á
C(2)Á
/
S(2)
74.36(7)
76.16(7)
104.15(8)
105.66(8)
103.02(7)
104.59(8)
83.0(4)
In 2 a carbonyl group bridges a RuÁ/Ru edge, which is
/
/
/
/S(2)
the shortest of the four RuÁRu edges (Ru3Á
/
/
Ru4
2.741(1) A) [7,33]. All the ruthenium atoms are also
/
/
/
/
Ru(4)
Ru(3)
Ru(4)
Ru(3)
˚
/
/
/
/
/
/
S(1)
S(2)
/
/
/
/
/
/
/
/
S(2)
/
/Ru(3)
/
/
S(2)
/
/Ru(3)
79.5(4)
bound to two terminal carbonyls. The diphosphine
˚
bridges the longest RuÁRu edge (2.834(1) A), forming
/
an eight membered ring. If the xylene moiety is excluded
the Ru1,Ru2,P1,P2,C17,C10 atoms adopt a boat con-
formation with P1 and P2 deviated respectively ofꢁ
/
˚
0.204(2) andꢁ0.261(2) A from the mean plane defined
/
by Ru1,Ru2,C10,C17; this plane forms a dihedral angle
of 85.3(1)8 with the xylene moiety (mean plane defined
by C10,C11,C12,C13,C14,C15,C16,C17) and a dihedral
angle of 53.0(1)8 with the mean plane defined by the four
metal atoms Ru1,Ru2,Ru3,Ru4. The presence of the
bridging ligand with a large bite (xylene moiety)
promotes the elongation of the Ru1Á
/
Ru2 edge [7,33].
S bond distances span from 2.459(2) to
˚
2.511(2) A in good agreement with those found in 1.
The RuÁ
/
Fig. 1. View of the molecular structure of cluster 1 with the atomic
labelling scheme. The thermal ellipsoids are drawn at the 30%
probability level.
˚
The Sꢀ ꢀ ꢀS separation is of 3.048(2) A [7].

142
D. Belletti et al. / Inorganica Chimica Acta 347 (2003) 137Á144
/
Table 3
Table 4
˚
˚
List of bond lengths (A) and bond angles (8) for 2×
/
0.5CH2Cl2
List of bond lengths (A) and bond angles (8) for 3
Bond lengths
Bond lengths
Ru(1)Á
Ru(1)Á
Ru(2)Á
Ru(3)Á
Ru(1)Á
Ru(1)Á
Ru(2)Á
Ru(2)Á
Ru(3)Á
Ru(3)Á
Ru(4)Á
/
Ru(4)
Ru(2)
Ru(3)
Ru(4)
S(1)
2.780(1)
2.834(1)
2.769(1)
2.741(1)
2.475(2)
2.485(2)
2.459(2)
2.483(2)
2.497(2)
2.511(2)
2.488(2)
Ru(4)Á
Ru(1)Á
Ru(2)Á
Ru(3)Á
Ru(4)Á
/
S(2)
P(1)
P(2)
C(7)
C(7)
2.508(2)
Ru(1)Á
Ru(2)Á
Ru(1)Á
Ru(1)Á
Ru(2)Á
Ru(2)Á
Ru(3)Á
Ru(3)Á
/
Ru(3)
Ru(3)
S(1)
2.935(1)
2.715(1)
2.362(2)
2.379(2)
2.385(2)
2.393(2)
2.415(2)
2.413(2)
Ru(1)Á
/
P(1)
P(2)
2.338(2)
2.337(2)
1.832(6)
1.837(5)
1.500(8)
1.407(8)
1.502(7)
/
/
2.305(2)
2.309(2)
2.052(6)
2.045(7)
1.843(6)
1.833(6)
1.159(7)
1.497(9)
1.405(9)
1.506(9)
/
Ru(1)Á
/
/
/
/
P(1)Á
P(2)Á
C(8)Á
C(9)Á
/
C(8)
/
/
/S(2)
/C(15)
/
/
/S(2)
/
C(9)
/S(2)
P(1)Á
P(2)Á
O(7)Á
C(10)Á
C(11)Á
C(16)Á
/
C(10)
/S(1)
/
C(14)
/S(1)
/C(17)
/S(2)
C(14)ÁC(15)
/
/S(2)
/C(7)
/S(1)
/S(1)
/
C(11)
C(16)
C(17)
Bond angles
Ru(2)ÁRu(3)Á
Ru(1)ÁS(1)Á
Ru(1)ÁS(1)Á
Ru(2)ÁS(1)Á
Ru(1)ÁS(2)Á
Ru(1)ÁS(2)Á
Ru(2)ÁS(2)Á
S(1)ÁRu(1)Á
/S(2)
/
/
/
Ru(1)
80.20(3) S(2)Á
100.01(6) S(2)Á
75.85(5) P(2)Á
68.78(5) C(8)Á
99.77(6) C(15)Á
75.50(5) C(9)ÁC(8)Á
68.88(5) C(14)ÁC(15)Á
78.90(5)
/
Ru(2)Á
Ru(3)Á
Ru(1)Á
P(1)ÁRu(1)
P(2)ÁRu(1)
P(1)
P(2)
/
S(1)
78.16(5)
77.20(5)
97.16(6)
/S(1)
/
/
/
Ru(2)
Ru(3)
Ru(3)
Ru(2)
Ru(3)
Ru(3)
S(2)
/
/
S(1)
Bond angles
Ru(4)ÁRu(1)Á
Ru(3)ÁRu(2)Á
Ru(4)ÁRu(3)Á
Ru(3)ÁRu(4)Á
P(1)ÁRu(1)Á
P(1)ÁRu(1)Á
P(2)ÁRu(2)Á
P(2)ÁRu(2)Á
S(1)ÁRu(1)Á
S(1)ÁRu(2)Á
S(1)ÁRu(3)Á
/
/
/
/
P(1)
/
/
Ru(2)
Ru(1)
Ru(2)
Ru(1)
88.66(2) S(1)Á
89.42(2) Ru(2)Á
90.79(3) Ru(1)Á
91.13(2) Ru(2)Á
94.30(6) Ru(1)Á
170.10(6) C(10)ÁP(1)Á
91.86(6) C(17)ÁP(2)Á
168.01(6) Ru(3)ÁC(7)Á
75.83(6) C(11)ÁC(10)Á
76.15(6) C(16)ÁC(17)Á
74.96(5)
/
Ru(4)Á
S(1)Á
S(1)Á
S(2)Á
S(2)Á
/
S(2)
75.18(6)
104.93(6)
104.92(6)
103.65(6)
104.20(6)
116.3(2)
116.4(2)
84.0(3)
/
/
/
/
117.97(19)
118.61(19)
113.4(4)
/
/
/
/
Ru(4)
Ru(3)
Ru(4)
Ru(3)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
113.8(4)
/
/
S(1)
S(2)
S(1)
S(2)
/
/
/
/
/
/
/
/Ru(1)
/
/
/
/Ru(2)
/
/
/
/Ru(4)
one of the metal atoms at the base of the pyramid, Ru1,
the two phosphorous atoms substituting two carbonyl
groups in equatorial positions; the bond distances Ru1Á
P1 and Ru1Á
The chelation of the diphosphine on Ru1 atom produces
a lenghtening of the Ru1ÁRu3 side of the cluster [9],
/
/
S(2)
S(2)
S(2)
/
/P(1)
115.0(5)
116.1(4)
/
/
/
/P(2)
/
/
/
˚
P2 are 2.337(2) and 2.338(2) A respectively.
/
A view of the structure of 3 is shown in Fig. 3 together
with atomic numbering scheme; selected bond distances
and angles are given in Table 4.
Compound 3 is a 50-electron nido cluster with the well
known M3S2 core [35,9], which can be described as a
square pyramid with two metal and two sulfur atoms
alternating in the basal plane and the third metal atom
at the apex of the pyramid. The diphosphine chelates
/
˚
˚
2.935(1) A, against 2.715(1) A of the Ru2ÁRu3 side. The
/
chelating diphosphine forms with Ru1 a seven-mem-
bered ring which presents a boat conformation, with the
Ru1, C9 and C14 atoms deviated in the same direction
over the mean plane defined by P1,P2,C8,C15 (the
deviations for Ru1, C9, C14 atoms are 0.693(1),
˚
1.170(1), 1.200(1) A, respectively).
A view of the structure of 4 is shown in Fig. 4 together
with atomic numbering scheme; selected bond distances
and angles are given in Table 5.
It presents a Ru3S core with the sulfur atom capping
the metal triangle, two sides of which are bridged by a
Fig. 3. View of the molecular structure of cluster 3 with the atomic
labelling scheme. The thermal ellipsoids are drawn at the 30%
probability level.
Fig. 4. View of the molecular structure of cluster 4 with the atomic
labelling scheme. The thermal ellipsoids are drawn at the 30%
probability level.

D. Belletti et al. / Inorganica Chimica Acta 347 (2003) 137Á
/144
143
Table 5
Data Centre, CCDC Nos. 185511Á
/
185514 compounds
˚
List of bond lengths (A) and bond angles (8) for 4
3, 2×0.5CH2Cl2, 1×
/
/
0.5CHCl3 and 4, respectively. Copies
of this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge, CB2
Bond lengths
Ru(1)Á
Ru(1)Á
Ru(2)Á
Ru(2)Á
Ru(1)Á
Ru(3)Á
Ru(1)Á
Ru(2)Á
Ru(2)Á
/
Ru(3)
Ru(2)
Ru(3)
S(1)
2.791(4)
2.877(4)
2.696(4)
2.459(9)
2.410(9)
2.422(10)
2.358(9)
2.384(10)
2.424(9)
Ru(1)Á
/
O(7)
2.423(17)
2.01(4)
1.89(3)
1.83(3)
1.27(4)
1.49(5)
1.62(5)
1.35(5)
1.51(5)
1EZ, UK (fax: ꢁ44-1223-336-033; e-mail: deposit@
/
/
Ru(3)Á
/
C(7)
/
P(1)Á
P(2)Á
O(7)Á
C(7)Á
C(8)Á
C(9)Á
/
C(8)
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
/
/C(15)
/
S(1)
/
C(7)
/
S(1)
/
C(34)
/
P(2)
/
C(9)
Acknowledgements
/
P(1)
/
C(14)
/
P(2)
C(14)ÁC(15)
/
Financial support from the Ministero dell’Universita`
e della Ricerca Scientifica e Tecnologica (Roma, Cofin
2000) is gratefully acknowledged. The facilities of
the Centro Interdipartimentale di Misure (Universita`
di Parma) were used to record the NMR and mass
spectra.
Bond angles
Ru(3)ÁRu(1)Á
Ru(3)ÁRu(2)Á
Ru(2)ÁRu(3)Á
P(2)ÁRu(1)Á
P(2)ÁRu(1)Á
P(2)ÁRu(1)Á
O(7)ÁRu(1)Á
P(2)ÁRu(1)ÁRu(2)
O(7)ÁRu(1)ÁRu(2)
P(1)ÁRu(2)Á
P(1)ÁRu(2)Á
P(2)ÁRu(2)Á
P(1)ÁRu(2)Á
/
/
Ru(2)
Ru(1)
Ru(1)
56.79(11) P(2)Á
60.01(11) P(1)Á
63.20(11) P(2)Á
85.4(3)
175.4(5)
110.9(2)
64.8(4)
/
Ru(2)Á
Ru(2)Á
Ru(2)Á
C(7)ÁRu(3)Á
C(8)ÁP(1)ÁRu(2)
C(15)ÁP(2)Á
C(15)ÁP(2)Á
Ru(1)ÁP(2)Á
C(7)ÁO(7)Á
O(7)ÁC(7)Á
O(7)ÁC(7)Á
C(34)ÁC(7)Á
C(9)ÁC(8)ÁP(1)
/
Ru(3)
Ru(1)
Ru(1)
112.0(2)
138.0(3)
52.0(2)
/
/
/
/
/
/
/
/
/
/
S(1)
/
/
Ru(1)
75.2(10)
119.4(11)
116.6(12)
120.4(11)
74.0(3)
/
/
O(7)
/
/
/
/
Ru(3)
/
/
Ru(1)
Ru(2)
/
/
Ru(3)
/
/
/
/
54.1(2)
/
/Ru(2)
/
/
121.5(4)
93.8(3)
/
/
Ru(1)
C(34)
Ru(3)
103.9(19)
108.0(3)
116.0(2)
136.0(3)
112.0(2)
References
/
/
P(2)
/
/
/
/
S(1)
106.0(3)
82.9(3)
/
/
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/
/
S(1)
/
/
Ru(3)
/
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Ru(3)
144.0(3)
/
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˚
triangle are the longest ones [2.791(4) and 2.877(4) A]
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/
/
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˚
2.53(4) A, Ru2Á
/
C4Á
/
˚
est side [2.696(4) A]. The three RuÁ
/
S bond distances
span from 2.410(9) to 2.459(9) A. Due to the loss of a
phenyl ring the phosphinoÁphosphido ligand is coordi-
nated to the Ru1 and Ru2 atoms in unusual manner: the
phosphido P2 atom asimetrically bridges the Ru1ÁRu2
P2 2.424(9) A] and parte-
cipates with P1 to the chelation of Ru2 [Ru2ÁP1
P2 2.424(9) A]. The migratory insertion
of a phenyl ring into the C7ÁO7 carbonyl group causes
the elongation of RuÁC and CÁO bond distances
˚
/
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/
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/
˚
side [Ru1Á
/
P2 2.358(9), Ru2Á
/
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/
˚
2.384(10), Ru2Á
/
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/
/
˚
[2.01(4) an 1.27(4) A, respectively] and the formation
of a benzoyl moiety bridging the Ru3 and Ru1 atoms
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P(Ph)C5H4FeC5H4PPh2}(m-OCPh)(CO)6] [32] showing
a Ru3Se core.
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/
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/
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