Synthesis and reactivities of the indenyl-ruthenium cluster [(η5-C9H7)Ru(μ-SEt)]3: Indenyl effect in the trinuclear ruthenium cluster

Article abstract of DOI:10.1016/S0022-328X(98)00778-5

The triruthenium cluster with bridging ethanethiolato and indenyl ligands [(η⁵-C₉H₇)Ru(μ-SEt)]₃ (2) was synthesized by heating the mononuclear indenyl complex [(η⁵-C₉H₇)Ru(SEt)(PPh₃) ₂] (1a) in toluene. Cluster 2 reacted with MeI to afford the S-methylated cluster [(η⁵-C₉H₇)₃Ru ₃(μ-SEt)₂(μ-SEtMe)]I·CH₂Cl ₂ (4a) with high stereoselectivity through the attack of MeI on the axial SEt group from the equatorial side. The PF₆^- salt of the cationic cluster [(η⁵-C₉H₇)₃Ru ₃(μ-SEt)₂(μ-SEtMe)][PF₆] was further converted into the cationic carbonyl complex [(η⁵-C₉H₇)₂Ru ₂(μ-SEt)(CO)₄][PF₆] (5) by treatment with CO at 50°C. The crystal structures of 4a and 5 were determined by X-ray diffraction study. When a THF solution of 2 was allowed to contact with atmospheric pressure of CO at room temperature, the trinuclear carbonyl cluster [(η⁵-C₉H₇)₃Ru ₃(μ-SEt)₃(μ-CO)(CO)] (6) and the dinuclear carbonyl complex [(η⁵-C₉H₇)Ru(μ-SEt)(CO)]₂ (7) were obtained. The structures of 6 and 7 were also crystallographically determined. Furthermore, cluster 2 was oxidized in refluxing CHCl₃ to give [(η⁵-C₉H₇)Ru(SEt)Cl]_n (9). The Cp analogue of 2, [CpRu(μ-SEt)]₃, failed to react with CO and CHCl₃, and the hapticity change of the indenyl ligand in 2 is considered to be crucial for the initial interaction of 2 with CO and CHCl₃. These reactions provide rare examples of the indenyl ligand effect in a multinuclear complex.

Full text of DOI:10.1016/S0022-328X(98)00778-5

Journal of Organometallic Chemistry 569 (1998) 99–108
Synthesis and reactivities of the indenyl-ruthenium cluster
[(p5-C9H7)Ru(v-SEt)]3: indenyl effect in the trinuclear ruthenium
cluster1
Tetsu Sato a, Masayuki Nishio b, Youichi Ishii b, Hiroshi Yamazaki a, Masanobu Hidai b,*
a Department of Applied Chemistry, Faculty of Science and Engineering, Chuo Uni6ersity, Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan
b Department of Chemistry and Biotechnology, Graduate School of Engineering, The Uni6ersity of Tokyo, Hongo, Bunkyo-ku,
Tokyo 113-8656, Japan
Received 18 March 1998
Abstract
The triruthenium cluster with bridging ethanethiolato and indenyl ligands [(p5-C9H7)Ru(v-SEt)]3 (2) was synthesized by heating
the mononuclear indenyl complex [(p5-C9H7)Ru(SEt)(PPh3)2] (1a) in toluene. Cluster 2 reacted with MeI to afford the
S-methylated cluster [(p5-C9H7)3Ru3(v-SEt)2(v-SEtMe)]I·CH2Cl2 (4a) with high stereoselectivity through the attack of MeI on the
axial SEt group from the equatorial side. The PF6− salt of the cationic cluster [(p5-C9H7)3Ru3(v-SEt)2(v-SEtMe)][PF6] was further
converted into the cationic carbonyl complex [(p5-C9H7)2Ru2(v-SEt)(CO)4][PF6] (5) by treatment with CO at 50°C. The crystal
structures of 4a and 5 were determined by X-ray diffraction study. When a THF solution of 2 was allowed to contact with
atmospheric pressure of CO at room temperature, the trinuclear carbonyl cluster [(p5-C9H7)3Ru3(v-SEt)3(v-CO)(CO)] (6) and the
dinuclear carbonyl complex [(p5-C9H7)Ru(v-SEt)(CO)]2 (7) were obtained. The structures of 6 and 7 were also crystallographically
determined. Furthermore, cluster 2 was oxidized in refluxing CHCl3 to give [(p5-C9H7)Ru(SEt)Cl]n (9). The Cp analogue of 2,
[CpRu(v-SEt)]3, failed to react with CO and CHCl3, and the hapticity change of the indenyl ligand in 2 is considered to be crucial
for the initial interaction of 2 with CO and CHCl3. These reactions provide rare examples of the indenyl ligand effect in a
multinuclear complex. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium; Indenyl ligand; Thiolato ligand; Cluster; X-ray crystal structure
1. Introduction
metals [4]. Previously, we prepared a series of multinu-
clear sulfido, hydrosulfido, and thiolato complexes of
ruthenium [5–7], which exhibited unique reactivities [8]
and catalytic activities [9] characteristic of their multin-
uclear cores. Although considerable efforts have re-
cently been devoted to the synthesis of ruthenium–
sulfur multinuclear complexes by several groups [5–
7,10], most of the compounds reported are those con-
taining Cp, Cp*, and their simple alkyl analogues
(Cp=p5-C5H5, Cp*=p5-C5Me5). However, these an-
cillary ligands have a strong tendency to take a p5-co-
ordination mode, and it is often difficult to generate a
vacant coordination site on the metal center by the ring
slippage of the Cp or Cp* ligand. Intrigued by the
The chemistry of sulfur-bridged multinuclear transi-
tion metal complexes is a subject under current scrutiny
owing not only to their structural diversity [1] but also
to their involvement in the active sites of metallo-
proteins [2] and relevance to the industrial hydrodesul-
furization catalysts [3]. During the last decade we have
been focusing our attention on syntheses and reactions
of sulfur-bridged complexes of groups 8–10 noble
* Corresponding author.
1 Dedicated to Professor Nakamura on the occasion of his retire-
ment from Osaka University.
0022-328X/98/$ - see front matter © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00778-5

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T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
possibility that use of the coordinatively more labile
ancillary ligands than Cp and Cp* ligands in this class
of complexes will lead to exploitation of their new
reactivities, we set out to synthesize multinuclear ruthe-
nium–sulfur complexes with indenyl ligands.
troscopically. The 1H-NMR spectrum of 2 exhibited
two distinct sets of signals in the ratio of 2:1 for each of
the indenyl and SEt groups. The SEt signal with the
larger relative intensity appeared as an ABX3 pattern (l
1.12 (t, 6H), 2.00 (dq, 2H), 2.02 (dq, 2H)) indicating the
diastereotopic nature of the methylene protons, while
the other SEt signal was observed as a common A2X3
pattern (l 0.84 (t, 3H), 2.47 (q, 2H)). Similarly, the set
of the indenyl signals with the larger relative intensity
(l 4.61 (m, 2H), 4.69 (m, 2H), 4.94 (t, 2H)) revealed
that these indenyl ligands are located in unsymmetric
The indenyl ligand has been known to undergo more
facile p5 to p3 ring slippage than the Cp and Cp*
ligands due to the accompanying aromatization of the
C6 ring, providing a vacant coordination site necessary
for further reactions [11]. By this effect, indenyl com-
plexes are often endowed with higher reactivities in
various types of ligand substitution and related reac-
tions in comparison with the corresponding Cp ana-
logues. Such ‘indenyl ligand effect’ has been attracting
great interest in recent years and well documented with
mononuclear complexes [12]. However, little has been
investigated with the indenyl ligand effect in clusters
[13]. In this paper, we describe synthesis of a thiolato-
bridged trinuclear ruthenium cluster with indenyl lig-
ands and its unique reactivities.
1
circumstances. These H-NMR features, as well as the
analytical data, suggest that complex 2 has a triangular
Ru3 core with one bridging SEt ligand on each edge,
where two of the SEt groups occupy equatorial posi-
tions with respect to the chair-like Ru3S3 ring, and the
third SEt group takes axial conformation (Eqn. 1). This
type of structure was also found in the related Cp
cluster [CpRu(v-SnPr)]3 (3) [14]. Assuming that the
structure of cluster 2 is analogous to that of 3, the 48e−
core of 2 has three Ru–Ru bonds. The molecular
structure of 2 was further supported by the diffraction
study of the S-methylation product from 2 (vide infra).
2. Results and discussion
2.1. Synthesis of the trinuclear indenyl cluster
[(p5-C9H7)Ru(v-SEt)]3
2.2. Reaction of [(p5-C9H7)Ru(v-SEt)]3 with MeI
We have previously reported that the thiolato-
bridged Ru(II)–Ru(II) dinuclear complex [Cp*Ru(v-
SiPr)2RuCp*] undergoes oxidative addition with alkyl
halides (RX) at the dinuclear center to give the corre-
sponding Ru(III)–Ru(III) complex [Cp*RuR(v-
SiPr)2RuXCp*] [7]. In contrast, the reaction of the
trinuclear cluster 2 with MeI afforded the S-methylated
cationic cluster [(p5-C9H7)3Ru3(v-SEt)2(v-SEtMe)]I
(4a) in good yield2.
Although our attempts to synthesize thiolato-bridged
dinuclear ruthenium complexes with indenyl ligands
were unfruitful, we succeeded in synthesizing the
triruthenium cluster with indenyl and bridging
ethanethiolato ligands, [(p5-C9H7)Ru(v-SEt)]3 (2).
Thus, the mononuclear indenyl complex [(p5-
C9H7)Ru(SEt)(PPh3)2] (1a) was first prepared from [(p5-
C9H7)RuCl(PPh3)2] by treatment with excess amounts
of NaSEt in refluxing THF. Heating a toluene solution
of complex 1a under reflux gave cluster 2 as a dark
purple microcrystalline solid in good yield with the
dissociation of PPh3.
This result is comparable with the reaction of the
Ir(II)–Ir(II) complex [Cp*Ir(v-SR)2IrCp*] (R=iPr, cy-
clohexyl) with MeOTf (OTf=OSO2CF3), which yielded
the
S-methylated
complex
[Cp*Ir(v-SR)(v-
SMeR)IrCp*][OTf] [15]. In complexes 2 and [Cp*Ir(v-
SR)2IrCp*] each metal center satisfies the effective
atomic number of 18e− by making two or one metal–
A similar method was already reported by Shaver and
co-workers for the synthesis of the analogous Cp clus-
i
ters [CpRu(v-SR)]3 (R=nPr, Pr) [14]. However, reac-
tions of some other alkane and arenethiolato complexes
[(p5-C9H7)Ru(SR)(PPh3)2] (1b, R=iPr; 1c, R=CH2Ph;
1d, R=4-MeC6H4) under similar conditions ended in
the formation of a complex mixture.
Cluster 2 is highly soluble in most common organic
solvents including hexane and was characterized spec-
2 Similar S-methylation was also observed with [CpRu(v-SEt)]3.
[Cp3Ru3(v-SEt)2(v-SEtMe)]I·CH2Cl2: yield 19%, 1H-NMR (CDCl3)
d 1.15 (t, 6H, J=7.3 Hz, SCH2Me), 1.44–1.65 (m, 4H, SCH2Me),
1.57 (t, 3H, J=7.3 Hz, MeSCH2Me), 2.58 (s, 3H, SCH3), 3.71 (q,
2H, J=7.3 Hz, MeSCH2Me), 5.03 (s, 5H, p5-C5H5), 5.17 (s, 10H,
p5-C5H5).

T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
101
Table 1
spectral and analytical data are also consistent with the
formulation in Eqn. 2. The molecular structure of 4a was
unambiguously determined by X-ray crystallography.
Selected bond distances and angles are listed in Table 1,
and an ORTEP drawing is depicted in Fig. 1.
Selected bond distances and angles for [(p5-C9H7)3Ru3(v-SEt)2(v-
SEtMe)]I·CH2Cl2 (4a·CH2Cl2)
˚
Distances (A)
Ru(1)–Ru(2)
Ru(2)–Ru(3)
Ru(1)–S(2)
Ru(2)–S(3)
Ru(3)–S(3)
Ru(1)–C(2)
Ru(1)–C(4)
Ru(2)–C(10)
Ru(2)–C(12)
Ru(2)–C(14)
Ru(3)–C(20)
Ru(3)–C(22)
2.741(1)
2.753(1)
2.280(2)
2.259(2)
2.256(2)
2.213(8)
2.189(8)
2.309(8)
2.176(8)
2.328(8)
2.178(7)
2.206(7)
Ru(1)–Ru(3)
Ru(1)–S(1)
Ru(2)–S(2)
Ru(3)–S(1)
Ru(1)–C(1)
Ru(1)–C(3)
Ru(1)–C(5)
Ru(2)–C(11)
Ru(2)–C(13)
Ru(3)–C(19)
Ru(3)–C(21)
Ru(3)–C(23)
2.728(1)
2.296(2)
2.295(2)
2.304(2)
2.401(8)
2.164(7)
2.402(8)
2.197(8)
2.207(8)
2.347(8)
2.174(7)
2.322(7)
In agreement with the formulation, cluster 4a is a
triangular cluster with two v-SEt and one v-SEtMe
ligands. The sulfur atoms are coordinated in mutually cis
configuration with respect to the Ru3 plane. The Ru–Ru
˚
distances (2.728–2.753 A) are indicative of the presence
of three Ru–Ru single bonds among the three ruthenium
atoms, being in accordance with the 48 valence electrons
of 4a. The three indenyl ligands are also mutually cis.
˚
The slip values (DM–C, 0.117–0.201 A), the hinge angles
(HA, 3.8–5.9°), and the fold angles (FA, 4.1–10.9°)
found in 4a are diagnostic of p5 coordination of the
indenyl ligands.3 The Et group of the SEtMe ligand is
located in the axial position, while the other SEt and
SMe groups occupy the equatorial positions. These
crystallographic results also strongly support the spec-
troscopically characterized structure of cluster 2.
Judging from the molecular structure, cluster 4a was
formed through the attack of MeI on the axial SEt group
from the equatorial side of 2. Interestingly, the 1H-NMR
analysis of the crude reaction mixture revealed that no
other stereoisomer than 4a is produced during the
reaction, indicating that the S-methylation of 2 proceeds
with very high stereoselectivity. This selectivity can be
accounted for by considering that the axial SEt group is
situated close to the lone pair on the other bridging
sulfur atoms and protects these sulfur atoms effectively
from attack by MeI from the axial side. In fact, it has
been reported that, in the molecular structure of 3, one
of the h-protons of the axial SnPr group is within the van
der Waals contact distance of the other sulfur atoms [14].
When the cationic indenyl cluster [(p5-C9H7)3Ru3(v-
SEt)2(v-SEtMe)][PF6] (4b), which was prepared by anion
metathesis of 4a with KPF6, was allowed to react with
CO at 50°C for 55 h, a new cationic carbonyl complex
[(p5-C9H7)2Ru2(v-SEt)(CO)4][PF6] (5) was obtained in
moderate yield.
Angles (°)
Ru(1)–Ru(2)
59.53(2)
60.01(3)
Ru(2)–Ru(1)–Ru(3)
S(1)–Ru(1)–S(2)
S(1)–Ru(3)
60.46(2)
81.98(7)
–Ru(3)
Ru(1)–Ru(3)
–Ru(2)
S(2)–Ru(2)–S(3) 88.26(7)
–S(3)90.48(7)
Ru(1)–S(2)–Ru(2)
Ru(1)–S(1)
72.73(6)
75.15(6)
73.61(7)
–Ru(3)
Ru(2)–S(3)
–Ru(3)
metal bonds, respectively, while the complex [Cp*Ru(v-
SiPr)2RuCp*] has two coordinatively unsaturated (16e−)
ruthenium centers. The difference in the electronic struc-
ture between 2 and [Cp*Ru(v-SiPr)2RuCp*] is probably
reflected in the reactivities toward MeI.
1
The H-NMR spectrum of cluster 4a exhibited a new
SMe singlet at l 2.94 in addition to the SEt and indenyl
signals similar to those described for cluster 2. Other
1
The H-NMR spectrum of 5 revealed that it contains
two equivalent indenyl ligands and one SEt ligand, and
3 DM–C for 4a represents [M–Cav(for C(1),C(5))]−[M–Cav(for
C(2),C(4))], [M–Cav(for C(10), C(14))]−[M–Cav(for C(11),C(13))],
and [M–Cav(for C(l9),C(23))]–[M–Cav(for C(20),C(22))]. HA repre-
sents the bending of the indenyl ligands at C(2)/C(4), C(11)/C(13),
and C(20)/C(22), and FA at C(1)/C(5), C(10)/C(14), and C(19)/C(23)
[16].
Fig. 1. An ORTEP drawing of the cationic part in [(p5-C9H7)3Ru3(v-
SEt)2(v-SEtMe)]I·CH2Cl2 (4a·CH2Cl2).

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T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
the trinuclear carbonyl cluster [(p5-C9H7)3Ru3(v-
SEt)3(v-Co)(CO)] (6) and the dinuclear carbonyl com-
plex [(p5-C9H7)Ru(v-SEt)(CO)]2 (7) were isolated from
the reaction mixture by chromatographic separation.
Both of the two compounds were characterized spectro-
scopically as well as crystallographically.
Similarly to cluster 2, cluster 6 showed two sets of
1H-NMR signals with the relative intensity of 2:1 for
each of the SEt and indenyl protons, suggesting that the
trinuclear core of 2 is maintained in 6. The IR spectra
revealed that cluster 6 contains a terminal (wCO, 1927
cm−1) and a bridging (wCO, 1748 cm−1) carbonyl lig-
and. The crystal structure of 6 is fully consistent with
these spectral data.
Fig. 2. An ORTEP drawing of the cationic part in [(p5-C9H7)2Ru2(v-
SEt)(CO)4][PF6] (5).
the IR spectrum exhibited four absorptions due to
terminally bound CO ligands at 1991, 2010, 2037 and
2058 cm−1. The molecular structure of 5 was further
confirmed by X-ray diffraction study. An ORTEP
drawing is depicted in Fig. 2, and selected bond dis-
tances and angles are given in Table 2. Complex 5
consists of two (p5-C9H7)Ru(CO)2 moieties linked by a
The unit cell in the crystal of 6 contained two crystal-
lographically independent molecules. ORTEP drawings
for the independent molecules of cluster 6 are given in
Fig. 3, and selected bond distances and angles are in
Table 3. The two molecules are significantly different in
the orientation of the indenyl ligands, but the structures
of the Ru3(v-SEt)3(v-CO)(CO) cores are essentially
equivalent except for the slight difference in the non-
bonding Ru–Ru distances. Cluster 6 is composed of
three (p5-C9H7)Ru fragments bridged by three SEt lig-
ands, and two of the ruthenium atoms are also bridged
by a CO ligand, while the third ruthenium center binds
a terminal CO ligand. The two CO ligands are mutually
trans with respect to the Ru3 plane. The doubly bridged
Ru–Ru contact in each molecule (2.7163(6), 2.7159(6)
˚
v-SEt bridge. The Ru–Ru separation at 4.166(1) A
excludes the presence of any bonding interaction be-
tween the two ruthenium atoms.
2.3. Reaction of [(p5-C9H7)Ru(v-SEt)]3 with CO
When a THF solution of cluster 2 was allowed to
contact with atmospheric pressure of CO at room tem-
perature, the starting 2 was consumed within 1 h, and
Table 2
Selected bond distances and angles for [(p5-C9H7)2Ru2(v-
SEt)(CO)4][PF6] (5)
˚
A) corresponds to a Ru–Ru single bond. The other
˚
˚
Ru–Ru distances (4.1179–4.1998 A) are significantly
Distances (A)
Ru(1)···Ru(2)
Ru(2)–S(1)
4.166(1)
2.408(3)
2.191(9)
2.216(9)
1.90(1)
2.335(9)
2.22(1)
2.331(9)
1.87(1)
Ru(1)–S(1)
Ru(1)–C(1)
Ru(1)–C(3)
Ru(1)–C(5)
Ru(1)–C(22)
Ru(2)–C(11)
Ru(2)–C(13)
Ru(2)–C(23)
2.392(3)
2.316(9)
2.181(9)
2.362(10)
1.837(10)
2.21(1)
long and demonstrate that two of the three Ru–Ru
bonds in 2 are cleaved on incorporation of two CO
molecules. The SEt group at the Ru–Ru single bond in
6 is oriented in an equatorial-like position, and the
other SEt groups axial. This conformation is in contrast
to the equatorial–equatorial–axial conformation of
SEt groups found in 2. It should also be pointed out
that the Cp analogues of cluster 6 [Cp3Ru3(v-SR)3(v-
CO)(CO)] (R=Me, Ph) were prepared by irradiation
of [CpRu(SR)(CO)2], but their molecular structures
have not been known [17]. These complexes are pre-
sumed to have the structures similar (or stereoisomeric)
to that found for 6.
Ru(1)–C(2)
Ru(1)–C(4)
Ru(1)–C(21)
Ru(2)–C(10)
Ru(2)–C(12)
Ru(2)–C(14)
Ru(2)–C(24)
2.23(1)
1.89(1)
Angles (°)
Ru(1)–S(1)
120.4(1)
S(1)–Ru(1)–C(21)
S(1)–Ru(2)–C(23)
91.4(3)
95.5(3)
–Ru(2)
S(1)–Ru(1)–C(22) 96.5(3)
S(1)–Ru(2)–C(24) 94.4(3)

T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
103
agreement with this solid state structure, showing the
p5-indenyl (l 4.39, t; 4.72, d) and SEt resonances (l
1.05, t; 2.54, q). The structural and spectral features
observed for 7 are comparable to related Cp* com-
plexes such as [Cp*Ru(v-StBu)(CO)]2 [18] and
[Cp*Fe(v-SEt)(CO)]2 [19].
In order to compare the reactivities of cluster 2 and
its Cp analogue [CpRu(v-SEt)]3 (8), reaction of 8 with
CO was also examined. As expected, cluster 8 was
recovered unchanged even after stirring for 3 days at
room temperature. The much higher reactivity of clus-
ter 2 is obviously ascribed to the presence of the indenyl
ligands, and we consider that the hapticity change of an
Table 3
Selected bond distances and angles for [(p5-C9H7)3Ru3(v-SEt)3(v-
CO)(CO)] (6)
˚
Distances (A)
Ru(1)–Ru(2)
Ru(2)···Ru(3)
Ru(1)–S(2)
Ru(2)–S(3)
Ru(3)–S(3)
Ru(1)–C(2)
Ru(1)–C(4)
Ru(1)–C(6)
Ru(2)–C(11)
Ru(2)–C(13)
Ru(2)–C(15)
Ru(3)–C(21)
Ru(3)–C(23)
Ru(3)–C(25)
Ru(4)–Ru(5)
Ru(5)···Ru(6)
Ru(4)–S(5)
2.7163(6)
4.1179(7)
2.374(1)
2.346(1)
2.359(1)
2.305(4)
2.170(4)
2.334(4)
2.378(4)
2.192(4)
2.388(4)
2.348(5)
2.220(6)
2.282(5)
2.7159(6)
4.1777(8)
2.390(1)
2.394(1)
2.384(1)
2.316(4)
2.184(4)
2.331(4)
2.327(4)
2.178(4)
2.313(4)
2.393(5)
2.175(4)
2.378(4)
Ru(1)···Ru(3)
Ru(1)–S(1)
Ru(2)–S(1)
Ru(3)–S(2)
Ru(1)–C(1)
Ru(1)–C(3)
Ru(1)–C(5)
Ru(2)–C(1)
Ru(2)–C(12)
Ru(2)–C(14)
Ru(3)–C(20)
Ru(3)–C(22)
Ru(3)–C(24)
4.1183(9)
2.334(1)
2.321(1)
2.372(1)
1.981(4)
2.197(4)
2.206(4)
2.025(4)
2.224(4)
2.216(4)
1.849(5)
2.275(6)
2.188(5)
Ru(4)···Ru(6)
Ru(4)–S(4)
Ru(5)–S(4)
4.1998(7)
2.342(1)
2.331(1)
2.401(1)
2.004(4)
2.203(4)
2.224(4)
1.997(4)
2.202(4)
2.198(4)
1.800(5)
2.231(4)
2.213(4)
Ru(5)–S(6)
Ru(6)–S(6)
Ru(6)–S(5)
Ru(4)–C(36)
Ru(4)–C(38)
Ru(4)–C(40)
Ru(5)–C(36)
Ru(5)–C(47)
Ru(5)–C(49)
Ru(6)–C(55)
Ru(6)–C(57)
Ru(6)–C(59)
Ru(4)–C(37)
Ru(4)–C(39)
Ru(4)–C(41)
Ru(5)–C(46)
Ru(5)–C(48)
Ru(5)–C(50)
Ru(6)–C(56)
Ru(6)–C(58)
Ru(6)–C(60)
Angles (°)
Fig. 3. ORTEP drawings of two independent molecules in the unit
Ru(2)–Ru(1)–S(2) 99.98(3)
Ru(1)–Ru(2)–S(3) 99.40(3)
cell of [(p5-C9H7)3Ru3(v-SEt)3(v-CO)(CO)] (6).
S(1)–Ru(1)–S(2)
S(2)–Ru(3)–S(3)
S(3)–Ru(2)–C(1)
86.26(4)
95.81(4)
85.3(1)
S(1)–Ru(2)–S(3)
S(2)–Ru(1)–C(1)
86.64(4)
86.0(1)
S(2)–Ru(3)–C(20) 93.8(1)
Ru(1)–S(1)–Ru(2) 71.39(3)
Ru(2)–S(3)–Ru(3) 122.15(5)
The molecular structure of the dinuclear carbonyl
complex 7 is shown in Fig. 4, and selected bond dis-
tances and angles are listed in Table 4. Complex 7 has
two (p5-C9H7)Ru(CO) fragments bridged by two SEt
ligands, where the SEt groups adopt syn configuration,
and both the indenyl and CO ligands are cis to each
other. The Ru2S2 core is puckered with a dihedral angle
of 162.5° around the Ru–Ru axis. There is no bonding
S(3)–Ru(3)–C(20) 94.9(1)
Ru(1)–S(2)–Ru(3) 120.39(5)
Ru(1)–C(1)–Ru(2) 85.4(2)
Ru(5)–Ru(4)–S(5) 99.18(3)
Ru(4)–Ru(5)–S(6) 100.05(3)
S(4)–Ru(4)–S(5)
S(5)–Ru(6)–S(6)
87.89(4)
94.57(4)
S(4)–Ru(5)–S(6)
87.55(4)
S(5)–Ru(4)–C(36) 85.1(1)
S(5)–Ru(6)–C(55) 92.8(1)
Ru(4)–S(4)–Ru(5) 71.06(3)
Ru(5)–S(6)–Ru(6) 121.93(4)
S(6)–Ru(5)–C(36) 86.4(1)
S(6)–Ru(6)–C(55) 94.7(1)
Ru(4)–S(5)–Ru(6) 122.48(4)
Ru(4)–C(36)–Ru(5) 85.5(2)
interaction between the two ruthenium atoms (Ru(1)–
1
˚
Ru(2), 3.6412(8) A). The H-NMR spectrum was in full

104
T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
Scheme 1.
Fig. 4. An ORTEP drawing of [(p5-C9H7)Ru(v-SEt)(CO)]2 (7).
CO. However, we must await further investigation to
elucidate the mechanism for the formation of dinuclear
complex 7. In any event, the reaction of cluster 2 with
CO is interesting in that it provides a rare example of
the indenyl ligand effect appeared in a multinuclear
complex.
indenyl ligand from p5- to p3-mode is essential for the
initial CO incorporation onto the cluster core. Based on
these observations, a proposed mechanism for the for-
mation of 6 from 2 is illustrated in Scheme 1. The
reaction is initiated by isomerization of an p5-indenyl
ligand into the p3-mode followed by the coordination
of a CO molecule to the vacant site generated. Isomer-
ization of the p3-indenyl ligand back to the p5-mode is
accompanied by the cleavage of the two Ru–Ru bonds.
Considering the axial–axial–equatorial conformation
of the SEt groups found in 6, inversion of the chair-like
conformation of the Ru3S3 six-membered ring should
also take place during the above process. Finally, an-
other CO molecule reacts with the unsaturated RuꢀRu
moiety to produce the final product 6. Since neither
complex 6 nor 7 underwent any further reaction with
CO at room temperature in THF, complexes 6 and 7
are supposed to be formed independently from 2 and
2.4. Reaction of [(p5-C9H7)Ru(v-SEt)]3 with CHCl3
Oxidation of cluster 2 took place on refluxing in
CHCl3 for 2 h, and a dark red Ru(III) complex formu-
lated as [(p5-C9H7)Ru(SEt)Cl]n (9) was isolated in 14%
yield.
Complex
9 was essentially the only diamagnetic
product detected by 1H-NMR analysis of the crude
reaction mixture. The characterization of 9 is based on
1
its H-NMR spectra exhibiting one set of indenyl and
SEt resonances and satisfactory analytical data (C, H,
S, and Cl). The diamagnetism and high symmetry re-
vealed by the H-NMR analysis seem to suggest that
Table 4
Selected bond distances and angles for 7
1
complex 9 has a dimeric structure (n=2). A related
Ru(III)–Ru(III) dinuclear complex [Cp*RuCl(v-
SEt)2RuCp*Cl] was previously prepared and found to
show similar 1H-NMR features due to its cis–syn struc-
ture [6].
In contrast, the reaction of the Cp analogue 8 in
refluxing CHCl3 was found to be sluggish. The conver-
sion was only 13% after 4 h, and an oxidation product
similar to 9 could not be isolated. In order to gain
insight into the difference in the reactivity, electrochem-
ical properties of clusters 2 and 8 were compared.
Interestingly, cyclic voltammogram measurements re-
vealed that each of the clusters 2 and 8 has a reversible
oxidation wave, where the oxidation potential of 2
˚
Distances (A)
Ru(1)–Ru(2)
Ru(1)–S(2)
Ru(2)–S(2)
Ru(1)–C(2)
Ru(1)–C(4)
Ru(1)–C(19)
Ru(2)–C(11)
Ru(2)–C(13)
Ru(2)–C(20)
3.6412(8)
2.384(1)
2.381(2)
2.213(6)
2.222(7)
1.792(6)
2.214(6)
2.214(6)
1.794(6)
Ru(1)–S(1)
Ru(2)–S(1)
Ru(1)–C(1)
Ru(1)–C(3)
Ru(1)–C(5)
Ru(2)–C(10)
Ru(2)–C(12)
Ru(2)–C(14)
2.377(2)
2.382(2)
2.341(7)
2.177(6)
2.342(8)
2.347(6)
2.163(6)
2.362(6)
Angles (°)
S(1)–Ru(1)–S(2) 79.15(5)
S(1)–Ru(1)–C(19) 94.7(2)
S(1)–Ru(2)–C(20) 92.4(2)
Ru(1)–S(1)–Ru(2) 99.83(6)
S(1)–Ru(2)–S(2)
S(2)–Ru(1)–C(19)
S(2)–Ru(2)–C(20)
Ru(1)–S(2)–Ru(2)
79.12(5)
92.0(2)
94.4(2)
99.66(5)

T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
105
(E1/2=0.30 V vs SCE, in CH2Cl2-0.1 M NBu4BF4) is
slightly higher than that of 8 (E1/2=0.20 V). The
discrepancy between the oxidation potentials and the
susceptibility to the oxidation by CHCl3 may be ex-
plained by the indenyl ligand effect in cluster 2. Al-
though the reaction mechanism has not been clarified,
the p5–p3 isomerization of an indenyl ligand in 2 would
play an important role in an early stage of the oxida-
tion process.
In conclusion, we have prepared a novel trinuclear
ruthenium cluster 2 with p5-indenyl and bridging thio-
lato ligands and demonstrated that this cluster shows
several interesting reactivities toward MeI, CO, and
CHCl3. In particular, the latter two reactions were not
observed with the corresponding Cp cluster 8, thus
providing rare examples showing the indenyl ligand
effect in a multinuclear complex.
NMR (C6D6):l 1.69 (t, 3H, J=7.4 Hz, SCH2Me), 2.57
(q, 2H, J=7.4 Hz, SCH2Me), 4.36 (d, 2H, J=2.0 Hz,
p5-C9H7), 5.26 (t, 1H, J=2.0 Hz, p5-C9H7), 6.94–7.52
(m, 34H, aryl); 31P{1H}-NMR (C6D6): l 49.88 (s).
Anal. Calc. for C48H46OP2SRu: C, 69.13; H, 5.56.
Found: C, 69.32; H, 5.58.
1b, 1c, and 1d were prepared by similar procedures
from [(p5-C9H7)RuCl(PPh3)2] and NaSiPr, NaSCH2Ph,
and NaS(4-MeC6H4), respectively.
1b: Dark green crystals from toluene-MeOH (77%).
1H-NMR (C6D6): l 1.71 (d, 6H, J=6.5 Hz, SCHMe2),
2.70 (sep, 1H, J=6.5 Hz, SCHMe2), 4.54 (br, 2H,
[(p5-C9H7), 5.20 (br, 1H, p5-C9H7), 6.90–7.83 (m, 34H,
aryl); 31P{1H}-NMR (C6D6): l 48.38 (s). Anal. Calc.
for C48H44P2SRu: C, 70.66; H, 5.44. Found: C, 70.39;
H, 5.65.
1c: Dark green crystals from toluene-MeOH (75%).
1H-NMR (C6D6): l 3.72 (s, 2H, SCH2Ph), 4.44 (d, 2H,
J=2.5 Hz, p5-C9H7), 5.27 (br, 1H, p5-C9H7), 6.89–7.48
(m, 39H, aryl); 31P{1H}-NMR (C6D6): l 50.14 (s).
Anal. Calc. for C52H44P2SRu: C, 72.29; H, 5.13. Found:
C, 71.97; H, 5.06.
3. Experimental section
3.1. General methods
1d: Dark green crystals from toluene-MeOH (82%).
1H-NMR (C6D6): l 2.29 (s, 3H, Me), 4.20 (d, 2H,
J=2.0 Hz, p5-C9H7), 5.30 (t, 1H, J=2.0 Hz, p5-C9H7),
6.91–7.75 (m, 38H, aryl); 31P{1H}-NMR (C6D6): l
47.88 (s). Anal. Calc. for C52H44P2SRu: C, 72.29; H,
5.13. Found: C, 72.15; H, 5.17.
All manipulations were carried out using standard
Schlenk tube techniques. [(p5-C9H7)RuCl(PPh3)2] [20]
and [(p5-C5H5)RuCl(PPh3)2] [21] were prepared accord-
ing to literature methods. Sodium thiolates were pre-
pared from the corresponding thiols and NaH. Solvents
were dried and distilled prior to use. Alumina for
column chromatography was purchased from Nacalai
Tesque (Alumina Activated 200). Other reagents were
commercially obtained and used without further purifi-
cation. IR spectra were recorded on a Shimadzu 8100M
spectrometer, while 1H- and 31P{1H}-NMR spectra
were obtained on a JEOL EX-270 spectrometer. Ele-
mental analyses were carried out on a Perkin-Elmer
2400II CHN analyzer. Electrochemical measurements
were made with Hokuto Denko instrumentation (HA-
501 potentiostat and HB-105 function generator) by
using a glassy carbon working electrode; potentials
were measured in CH2Cl2-0.1 M [Bu4N][BF4] versus an
SCE.
3.3. Preparation of [(p5-C9H7)Ru(v-SEt)]3 (2)
A dark green solution of 1a (253 mg, 0.315 mmol) in
toluene (20 ml) was stirred at 100°C for 2 days. The
purple brown solid obtained by evaporation of the
solvent under reduced pressure was dissolved in
toluene/hexane (1/1) and loaded on an activated alu-
mina column. The column was washed with toluene/
hexane (1/1) to remove PPh3, and then a dark purple
band eluted with toluene was collected. The eluate was
dried up, and the residue was recrystallized from THF-
MeOH to give 2 as a dark purple microcrystalline solid
1
(45.2 mg, 0.0543 mmol, 52%). H-NMR (C6D6): l 0.84
(t, 3H, J=7.3 Hz, SCH2Me), 1.12 (t, 6H, J=7.5 Hz,
SCH2Me), 2.00 (dq, 2H, J=11.9 Hz, 7.5 Hz,
SCH2Me), 2.02 (dq, 2H, J=11.9 Hz, 7.5 Hz,
SCH2Me), 2.47 (q, 2H, J=7.3 Hz, SCH2Me), 4.61 (m,
2H, p5-C9H7), 4.68 (d, 2H, J=2.5 Hz, p5-C9H7), 4.69
(m, 2H, p5-C9H7), 4.91 (t, 1H, J=2.5 Hz, p5-C9H7),
4.94 (t, 2H, J=2.5 Hz, p5-C9H7), 6.90–7.49 (m, 12H,
aryl). Anal. Calc. for C33H36S3Ru3: C, 47.64; H, 4.36.
Found: C, 47.91; H, 4.54.
3.2. Preparation of [(p5-C9H7)Ru(SR)(PPh3)2] (R=Et
i
(1a), Pr (1b), CH2Ph (1c), 4-MeC6H4 (1d))
The following procedure for the preparation of 1a
(R=Et) is representative. To an orange solution of
[(p5-C9H7)RuCl(PPh3)2] (498 mg, 0.642 mmol) in THF
(35 ml) was added NaSEt (223 mg, 2.66 mmol), and the
mixture was allowed to reflux for 15 min. Rapid color
change from orange to purple was observed. The sol-
vent was removed in vacuo, and the resulting dark
green solid was extracted with toluene. Addition of
MeOH to the concentrated extract gave 1a·MeOH as
3.4. Preparation of
[(p5-C9H7)3Ru3(v-SEt)2(v-SEtMe)][I] (4a)
To a solution of 2 (1.00 g, 1.20 mmol) in THF (30
ml) was added MeI (0.570 g, 3.94 mmol), and the
1
dark green crystals (395 mg, 0.474 mmol, 74%). H-

106
T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
mixture was stirred at 50°C for 20 h. During this period
the initial dark purple solution turned to a dark brown
suspension. The solvent was removed in vacuo, and the
residue was washed with benzene and dissolved in
CH2Cl2. Addition of hexane to the CH2Cl2 solution
gave 4a as a dark brown powder (985 mg, 1.01 mmol,
7.47–7.62 (m, 8H, aryl). Anal. Calc. for
C24H19O4F6PSRu2: C, 38.41; H, 2.55. Found: C, 38.21;
H, 2.82.
3.7. Preparation of
[(p5-C9H7)3Ru3(v-SEt)3(v-CO)(CO)] (6) and
[(p5-C9H7)Ru(v-SEt)(CO)]2 (7)
1
84%), whose H-NMR analysis indicated that it con-
tains no CH2Cl2 molecule. Crystalline samples of
4a·CH2Cl2 for X-ray diffraction study and elemental
analysis were obtained by slow diffusion of hexane into
a CH2Cl2 solution of 4a. A similar reaction at room
temperature for 3 days also gave 4a in 66% yield.
CO gas was bubbled into a solution of 2 (0.203 g,
0.244 mmol) in THF (7 ml) for 15 min and the solution
was further stirred under a CO atmosphere for 1 h at
room temperature. During this period the color of the
solution changed from dark purple to brown. After
removal of the solvent under reduced pressure, the
resulting solid was dissolved in benzene and loaded on
an activated alumina column. The first reddish yellow
band eluted with benzene and the second dark red band
eluted with THF were collected. Each fraction was dried
up, and the resulting solids were recrystallized from
benzene-MeOH to give 7 as red crystals (44 mg, 0.0720
mmol, 20%) and 6 as black crystals (70 mg, 0.0789
mmol, 32%), respectively. 6: IR (KBr disk, cm−1): 1748,
1H-NMR (CDCl3):
l 0.62 (t, 3H, J=7.3 Hz,
MeSCH2Me), 1.22 (t, 6H, J=7.3 Hz, SCH2Me), 2.25
(m, 4H, SCH2Me), 2.51 (q, 2H, J=7.3 Hz,
MeSCH2Me), 2.94 (s, 3H, SCH3), 4.50 (m, 2H, p5-
C9H7), 4.55 (t, 2H, J=2.6 Hz, p5-C9H7), 5.23 (d, 2H,
J=2.6 Hz, p5-C9H7), 5.79 (t, 1H, J=2.6 Hz, p5-C9H7),
5.97 (m, 2H, p5-C9H7), 7.25-7.47 (m, 10H, aryl), 7.97 (d,
2H, J=8.6 Hz, aryl). Anal. Calc. for C35H41S3Cl2Ru3I:
C, 39.70; H, 3.90. Found: C, 40.01; H, 3.85.
1
3.5. Preparation of
1927 [w(CO)]. H-NMR (C6D6): l 1.09 (t, 6H, J=7.4
[(p5-C9H7)3Ru3(v-SEt)2(v-SEtMe)][PF6] (4b)
Hz, SCH2Me), 1.29 (t, 3H, J=7.4 Hz, SCH2Me), 1.64
(dq, 2H, J=12.8, 7.4 Hz, SCH2Me), 2.25 (q, 2H,
J=7.4 Hz, SCH2Me), 2.43 (dq, 2H, J=12.8, 7.4 Hz,
SCH2Me), 4.41 (m, 2H, p5-C9H7), 5.07 (t, 2H, J=2.6
Hz, p5-C9H7), 5.08 (t, 1H, J=2.6 Hz, p5-C9H7), 5.24 (d,
2H, J=2.6 Hz, p5-C9H7), 5.55 (m, 2H, p5-C9H7), 6.75–
7.38 (m, 12H, aryl). Anal. Calc. for C35H36O2S3Ru3: C,
47.34; H, 4.09. Found: C, 47.06; H, 3.95. 7: IR (KBr
To a solution of 4a (271 mg, 0.278 mmol) in CH2Cl2
(40 ml) was added KPF6 (517 mg, 2.81 mmol), and the
mixture was stirred at room temperature for 1 week.
The solvent was removed in vacuo, and the resulting
dark brown solid was extracted with CH2Cl2. Addition
of hexane to the concentrated extract gave 4b·CH2Cl2
1
1
disk, cm−1): 1896, 1923 [w(CO)]. H-NMR (C6D6): l
as black crystals (240 mg, 0.223 mmol, 80%). H-NMR
(CDCl3): l 0.61 (t, 3H, J=6.9 Hz, MeSCH2Me), 1.22
(t, 6H, J=7.6 Hz, SCH2Me), 2.24 (m, 4H, SCH2Me),
2.51 (q, 2H, J=6.9 Hz, MeSCH2Me), 2.62 (s, 3H,
SCH3), 4.46 (m, 2H, p5-C9H7), 4.50 (t, 2H, J=2.3 Hz,
p5-C9H7), 5.20 (d, 2H, J=2.3 Hz, p5-C9H7), 5.25 (m,
2H, p5-C9H7), 5.79 (t, 1H, J=2.3 Hz, p5-C9H7), 7.29–
7.51 (m, 10H, aryl), 7.69 (d, 2H, J=8.6 Hz, aryl). Anal.
Calc. for C35H41F6PS3Cl2Ru3: C, 39.03; H, 3.84. Found:
C, 39.36; H, 3.88.
1.05 (t, 6H, J=7.3 Hz, SCH2Me), 2.54 (q, 4H, J=7.3
Hz, SCH2Me), 4.39 (t, 2H, J=2.5 Hz, p5-C9H7), 4.72
(d, 4H, J=2.5 Hz, p5-C9H7), 6.93–7.20 (m, 8H, aryl).
Anal. Calc. for C24H24O2S2Ru2: C, 47.20; H, 3.96.
Found C, 47.13; H, 4.03.
3.8. Preparation of [(p5-C5H2)Ru(v-SEt)]3 (8)
To a solution of [(p5-C5H2)RuCl(PPh3)2] (1.00 g, 1.38
mmol) in THF (70 ml) was added NaSEt (0.41 g, 4.88
mmol), and the mixture was allowed to reflux for 15
min. Rapid color change from yellow to reddish brown
was observed. The solvent was removed in vacuo, and
the resulting solid was extracted with toluene. The
extract was dried up, and the residue was recrystallized
from THF-MeOH to give [(p5-C5H2)Ru(SEt)(PPh3)2] as
a red crystalline solid (0.406 g, 0.541 mmol, 39%).
1H-NMR (C6D6): l 1.63 (t, 3H, J=7.3 Hz, SCH2Me),
2.46 (q, 2H, J=7.3 Hz, SCH2Me), 4.40 (s, 5H, p5-
C5H2), 6.97–7.84 (m, 30H, aryl); 31P{1H}-NMR (C6D6):
l 41.57 (s). Anal. Calc. for C43H40P2SRu: C, 68.69; H,
5.36. Found: C, 68.67; H, 5.58.
3.6. Preparation of [(p5-C9H7)2Ru2(v-SEt)(CO)4][PF6]
(5)
CO gas was bubbled into a solution of 4b (58.0 mg,
0.0539 mmol) in CH2ClCH2Cl (10 ml) at room temper-
ature for 30 min and the solution was further stirred at
50°C under a CO atmosphere for 55 h. During this
period the color of the solution changed from dark
brown to orange. The solvent was removed in vacuo,
and the resulting solid was washed with benzene and
recrystallized from CH2Cl2-ether to give 5 as orange
crystals (13.7 mg, 0.0183 mmol, 34%). IR (KBr disk,
cm−1): 1991, 2010, 2037, 2058 [w(CO)]. 1H-NMR
(C6D6): l 0.63 (t, 3H, J=7.3 Hz, SCH2Me), 1.64 (q,
2H, J=7.3 Hz, SCH2Me), 5.87 (m, 6H, p5-C9H7),
A red solution of [(p5-C5H2)Ru(SEt)(PPh3)2] (1.23 g,
1.63 mmol) in toluene (50 ml) was allowed to reflux for
6 h. The brown solid obtained by evaporation of the

T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
107
Table 5
X-ray crystallographic data for 4a·CH2Cl2, 5, 6, and 7
4a·CH2Cl2
5
6
7
Formula
Molecular weight
Space group
C35H41S3Cl2Ru3I
1058.91
P21/c
C24H19O4F6PSRu2
750.58
P21/a
C35H36O2S3Ru3
888.06
C24H24O2S2Ru2
610.71
C2/c
(
P1
Crystal system
Crystal color
Monoclinic
Dark brown
0.25×0.25×0.30
11.099(3)
27.569(4)
12.862(4)
Monoclinic
Orange
0.20×0.30×0.30
14.319(2)
12.223(2)
15.622(1)
Triclinic
Black
Monoclinic
Orange
0.30×0.60×0.30
16.811(3)
10.594(3)
28.392(5)
Crystal dimensions (mm)
0.20×0.20×0.80
11.010(2)
17.203(2)
19.829(3)
107.756(9)
103.401(9)
99.745(9)
3360.5(9)
4
1.755
1768
15.48
5B2qB50
32
˚
a (A)
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
107.78(2)
101.007(8)
110.10(2)
3
˚
V (A )
3747(1)
4
1.877
2072
23.52
5B2qB50
32
2683.8(6)
4
1.857
1472
13.34
5B2qB55
32
4717(1)
8
1.720
2432
14.76
5B2qB50
32
Z
Dcalc. (g cm−l
F(000)
)
v(Mo–Kh) (cm−1
2q range (°)
)
Scan speed (° min−1
)
Number of unique reflections
6747
6459
11825
4725
Transmission factors
Number of reflections used [I\3|(I)]
0.77–1.00
4237
0.84–1.00
3136
0.91–1.00
9405
0.81–1.00
3116
Number of variables
397
347
776
0.026
0.020
2.08
281
Ra
0.038
0.027
1.52
0.051
0.036
2.04
0.034
0.026
2.12
Rwb
GOFc
−3
˚
Maximum residual density, e A
0.84
0.69
0.77
0.57
a R=SꢀFoꢁ−ꢁFcꢀ/SꢁFoꢁ.
b Rw=[Sw(ꢁFoꢁ−ꢁFcꢁ)2/SwFo2]1/2, w=1/|2(Fo).
c GOF=[Sw(ꢁFoꢁ−ꢁFcꢁ)2/(Nobs−Nparams)]1/2
.
solvent under reduced pressure was dissolved in
toluene/hexane (1/1) and loaded on an activated alu-
mina column. The column was washed with toluene/
hexane (1/1) to remove PPh3, and then the reddish
yellow band eluted with THF/hexane (1/1) was col-
lected. The eluate was dried up, and the residue was
extracted with benzene/hexane (1/1). The solvent was
removed in vacuo, and the resulting solid was recrystal-
lized from THF-hexane to give 8 as dark brown crystals
(0.251 g, 0.368 mmol, 68%). 1H-NMR (C6D6): l 1.12 (t,
6H, J=7.3 Hz, SCH2Me), 1.28 (m, 4H, SCH2Me),
1.55 (t, 3H, J=7.3 Hz, SCH2Me), 3.52 (q, 2H, J=7.3
Hz, SCH2Me), 4.58 (s, 10H, p5-C5H2), 4.61 (s, 5H,
p5-C5H2). Anal. Calc. for C21H30S3Ru3: C, 36.99; H,
4.43. Found: C, 37.06; H, 4.58.
up, and the residue was recrystallized from acetone-
hexane to give 9 as brown powder (76.2 mg, 14%).
1H-NMR (CDCl3):
l 1.07 (t, 3H, J=7.4 Hz,
SCH2Me), 2.41 (q, 2H, J=7.4 Hz, SCH2Me), 4.35 (t,
1H, J=2.3 Hz, p5-C9H7), 5.31 (d, 2H, J=2.3 Hz,
p5-C9H7), 7.49–7.54 (m, 2H, aryl), 7.64–7.68 (m, 2H,
aryl). Anal. Calc. for C11H12SClRu: C, 42.24; H, 3.87;
S, 10.25; Cl, 11.33. Found: C, 41.73; H, 3.87; S, 10.04;
Cl, 11.93.
3.10. X-ray crystallographic studies
Single crystals of 4a·CH2Cl2, 5, 6, and 7 were sealed
in glass capillaries under an argon atmosphere and used
for data collection. Diffraction data were collected on a
Rigaku AFC7R four-circle automated diffractometer
with graphite-monochromatized Mo–Kh radiation
3.9. Preparation of [(p5-C9H7)Ru(SEt)Cl]n (9)
˚
(u=0.71069 A) at room temperature using the ꢀ-2q
A solution of 2 (499 mg, 0.600 mmol) in CHCl3 (35
ml) was heated under reflux for 4 h. Rapid color change
from purple to brown was observed. The brown solid
obtained by evaporation of the solvent under reduced
pressure was dissolved in THF and loaded on an
activated alumina column. The reddish brown band
eluted with THF was collected. The eluate was dried
scan technique for 4a·CH2Cl2 and 5, 6, and 7. The
orientation matrices and unit cell parameters were de-
termined by least-squares refinement of 25 machine
cantered reflections with 30.7°B2qB39.9° for
4a·CH2Cl2, 28.9°B2qB29.9° for 5, 39.8°B2qB40.0°
for 6, and 22.3°B2qB24.4° for 7. Intensity data were
corrected for Lorentz and polarization effects and for

108
T. Sato et al. / Journal of Organometallic Chemistry 569 (1998) 99–108
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absorption (empirical, C scans). For all crystals, no
significant decay was observed for three standard reflec-
tions monitored every 150 reflections during the data
collection.
The structure solution and refinements were carried
out by using the teXsan crystallographic software pack-
age [22]. The positions of the non-hydrogen atoms were
determined by Patterson methods (DIRDIF PATTY)
[23] and subsequent Fourier syntheses. All non-hydro-
gen atoms were refined by full-matrix least-squares
techniques with anisotropic thermal parameters. Hy-
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and were included in the final stage of the refinement
with fixed isotropic parameters. In the structure refine-
ment of 7, one of the SEt groups was found to be
disordered. Two methyl carbon atoms attached to
C(21) in the SEt group were placed at the two disor-
dered positions and refined as C(22) and C(25) with
0.667 and 0.333 occupancies, respectively. Details of the
X-ray diffraction study are summarized in Table 5.
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4. Supplementary material available
[10] For example (a) A. Venturelli, T.B. Rauchfuss, A.K. Verma,
Inorg. Chem. 36 (1997) 1360. (b) Q. Feng, T.B. Rauchfuss, S.R.
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Tables of atomic coordinates, anisotropic tempera-
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bond distances and angles for 4a·CH2Cl2, 5, 6, and 7
(54 pages) as well as listings of observed and calculated
structure factors for 4a·CH2Cl2, 5, 6, and 7 (137 pages)
are available from M.H. upon request.
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Gonza´lez-Bernardo, B. Mart´ın-Vaca, Organometallics 16 (1997)
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Acknowledgements
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(c) L. Mantovani, A. Ceccon, A. Gambaro, S. Santi, P. Ganis,
A. Venzo, Organometallics 16 (1997) 2682.
This work was supported by a Grant-in-aid for Spe-
cially Promoted Research (09102004) from the Ministry
of Education, Science, Sports, and Culture, Japan.
[14] A. Shaver, P.-Y. Plouffe, D.C. Liles, E. Singleton, Inorg. Chem.
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Acta 265 (1997) 59.
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