Synthesis of the first non-carbonyl cisoid fulvalene complexes with and Ru-Ru bond bridged by thiolate ligands

Article abstract of DOI:10.1039/b207928n

The addition of PPh₃ to a solution which was produced by the oxidation of [(η⁵-Cp)Ru(μ₂-η⁶:η⁶-C ₁₀H₈)Ru(η⁵-Cp)]²⁺- (BF₄^-)₂ (1) with p-benzoquinone and BF₃·OEt₂ (abbreviated as p-Bq/BF₃) in CH₂Cl₂-CH₃CN and subsequent Zn-reduction gave the transoid Ru-Fv complex (Fv = fulvalene) formulated as [(CH₃CN)₂(PPh₃)Ru(μ₂- η⁵:η⁵-C₁₀H₈) Ru(PPh₃)(CH₃CN)₂]²⁺ (BF₄^-)₂ (2a) in high yield as stable yellow crystals. Treatment of 2a with excess aryl thiols (ArSH; Ar = C₆H₅, p-CH₃C₆H₄ and p-ClC₆H₄), their thiolates and aryl dithiols (1,2-benzenedithiol or 3,4-toluenedithiol) or their dithiolates at room temperature afforded the Ru-Fv complexes bridged by thiolate ligands formulated as [(PPh₃)Ru(μ₂-η⁵:η⁵- C₁₀H₈) (μ₂-SAr)₂Ru(PPh₃)]²⁺ (BF₄^-)₂ (3a-c), (ArS)Ru(μ₂-η⁵:η⁵-C₁₀ H₈)(μ₂-SAr)₂Ru(SAr) (4a-c) and [(PPh₃)Ru(μ₂-η⁵:η⁵- C₁₀H₈) (μ₂-S₂C₆H₃R) Ru(PPh₃)]²⁺(BF₄^-)₂ (5a; R = H, 5b; R = CH₃), in high yield, respectively. Treatment of 2a with excess tert-butylthiolate produced the complex [(PPh₃)Ru(μ₂-η⁵:η⁵- C₁₀H₈) (μ₂-S^tBu)₂Ru]²⁺ (BF₄^-)(S^tBu^-) (6a). In contrast with complexes 2-5, a coordinatively unsaturated Ru atom was found in 6a, which is probably formed owing to the bulkiness of the ^tBuS^- ligand. X-Ray analysis of complexes 3-6 showed the presence of an Ru^III-Ru^III single bond.

Full text of DOI:10.1039/b207928n

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Synthesis of the first non-carbonyl cisoid fulvalene complexes with
an Ru–Ru bond bridged by thiolate ligands
Masanobu Watanabe,*a Masaru Sato*a and Masahiro Kaib
a Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570,
Japan. E-mail: wata@se.catv.ne.jp, msato@chem.saitama-u.ac.jp
b Faculty of Engineering, Tokyo Institute of Polytechnics, Atsugi, Kanagawa 243-0297, Japan
Received 13th August 2002, Accepted 2nd December 2002
First published as an Advance Article on the web 20th January 2003
The addition of PPh3 to a solution which was produced by the oxidation of [(η5-Cp)Ru(µ2-η6:η6-C10H8)Ru(η5-Cp)]2ϩ
(BF4Ϫ)2 (1) with p-benzoquinone and BF3ؒOEt2 (abbreviated as p-Bq/BF3) in CH2Cl2–CH3CN and subsequent
Zn-reduction gave the transoid Ru–Fv complex (Fv = fulvalene) formulated as [(CH3CN)2(PPh3)Ru(µ2-η5:η5-
C10H8)Ru(PPh3)(CH3CN)2]2ϩ(BF4Ϫ)2 (2a) in high yield as stable yellow crystals. Treatment of 2a with excess aryl
thiols (ArSH; Ar = C6H5, p-CH3C6H4 and p-ClC6H4), their thiolates and aryl dithiols (1,2-benzenedithiol or
3,4-toluenedithiol) or their dithiolates at room temperature afforded the Ru–Fv complexes bridged by thiolate
ligands formulated as [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-SAr)2Ru(PPh3)]2ϩ(BF4Ϫ)2 (3a–c), (ArS)Ru(µ2-η5:η5-C10H8)-
(µ2-SAr)2Ru(SAr) (4a–c) and [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-S2C6H3R)Ru(PPh3)]2ϩ(BF4Ϫ)2 (5a; R = H, 5b; R = CH3),
in high yield, respectively. Treatment of 2a with excess tert-butylthiolate produced the complex [(PPh3)Ru(µ2-η5:η5-
C10H8)(µ2-StBu)2Ru]2ϩ(BF4Ϫ)(StBuϪ) (6a). In contrast with complexes 2–5, a coordinatively unsaturated Ru atom
was found in 6a, which is probably formed owing to the bulkiness of the tBuSϪ ligand. X-Ray analysis of complexes
3–6 showed the presence of an RuIII–RuIII single bond.
-
Introduction
The chemistry of the dimetallafulvalene (M2Fv) complexes has
been attractive field of investigation, because the fulvalene
ligand can coordinate two transition metals in the adjacent
positions, which can induce novel reactivity and enforce unusual
structural features. Although a large number of carbonyl
dimetallafulvalene complexes have been reported by Vollhardt
and coworkers,1 those of non-carbonyl dimetallafulvalene
complexes are less,2–9 because of the lack of good precursor for
such complexes. The cisoid M2Fv complexes are considered as
potential model complexes for investigating catalytic sur-
faces.10,11 Recently, we reported an Ru2Fv complex with novel
coordination mode which was prepared by the oxidation of
biruthenocene with p-Bq/BF3 in good yield.12 We report here
Ϫ
that complex [(η5-Cp)Ru(µ2-η6:η6-C10H8)Ru(η5-Cp)]2ϩ(BF4
)
2
(1) is a very attractive and convenient starting material for
preparing various non-carbonyl cisoid Ru2Fv complexes
(Scheme 1).
Results and discussion
Fig. 1 ORTEP drawing of the cation [(CH3CN)2(PPh3)Ru(µ2-η5:η5-
C10H8)Ru(PPh3)(CH3CN)2]2ϩ (2b2ϩ) showing 50% probability level of
the thermal ellipsoids and the atom numbering scheme. For clarity all
hydrogen atoms are omitted.
Preparation of transoid bis(phosphine) complex 2a
The oxidation of 1 with p-Bq/BF3 at Ϫ30 ЊC, addition of excess
PPh3, and subsequent Zn-reduction gave an orange crystalline
complex 2a in high yield. Complex 2a was well soluble in
CH3CN, CH3COCH3 and CH3NO2 giving yellow solutions. In
with the whole molecular located on an inversion center. The
Fv ligand is perfectly planar and this is in sharp contrast with
the complexes 3–6 discussed below. From the ORTEP drawing
of 2b, the interesting elimination of two Cp rings and the
coordination of PPh3 and CH3CN to the Ru center are verified
and the complex 2b is formulated as [(CH3CN)2(PPh3)RuII-
(µ2-η5:η5-C10H8)RuII(PPh3)(CH3CN)2]2ϩ(PF6Ϫ)2, which adopts a
transoid arrangement of the Ru atoms towards the Fv ligand,
like the case of 1 and biruthenocene. It is noteworthy that the
loss of the Cp-ring from the complex 1 takes place easily under
such mild conditions, and 2 is the first non-carbonyl half
sandwich Ru2Fv complex. The half moiety of the molecule,
(C5H4)RuII(PPh3)(CH3CN)2]ϩ, is fundamentally similar to
other three-legged piano-stool complexes and the Ru–N
(2.063(7), 2.069(6) Å) and Ru–P (2.340(2) Å) distances corre-
spond with the reported values of analogous molecules.13 The
1
the H NMR spectrum of 2a in CD3NO2, no Cp signal was
observed, while two signals for the Fv ligand appeared at δ 4.36
and 4.76. The phenyl protons of PPh3 and the methyl protons
of CH3CN were also observed at δ 7.5–7.3 and 2.08, respect-
ively. In the 31P NMR spectrum of 2a, the phosphine ligand was
found at δ 50.7, which corresponds with the reported analo-
gous complex RuCp(CH3CN)2(PPh3)ϩ (δ 51.7) with a RuII–P
bond.13a In combination with the results of the elemental analy-
sis, 2a may be assigned as FvRu2(CH3CN)4(PPh3)2(BF4)2.
To obtain well formed single crystals, 2a was recrystallized
from CH3CN–Et2O in the presence of NH4PF6 and the X-ray
analysis of the obtained complex 2b was carried out. Selected
bond distances and angles are shown in Table 1. As can be seen
in Fig. 1, half of the molecule is crystallographically unique
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
D a l t o n T r a n s . , 2 0 0 3 , 6 5 1 – 6 5 8
651

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Scheme 1
average Ru–C(1–5) distance (2.123 Å) of 2b corresponds
with the values of the related half sandwich RuII–Cp complexes
such as [RuCp(CH3CN)2PMe3]ϩ (2.177(5) Å)13a and RuCp-
(CH3CN)3ϩ (2.135(3) Å).13d
other nucleophiles. To extend the Ru2Fv chemistry, the com-
plexes 2a and 2b are useful as more labile precursors to syn-
thesize a new series of Ru2Fv complexes, because CH3CN in 2
may be easily substituted by other nucleophiles such as halides
or thiolates. So, the reactions of 2 with some typical thiols and
thiolates were at first selected to verify the possibility mentioned
above. As the thiolate ligands have a high ability to bridge two
metal atoms, the formation of some cisoid Ru2Fv complexes
may be expected.
A plausible mechanism to explain the formation of 2a is
shown in Scheme 2. Complex 1 is soluble in CH3CN giving
the mixed valence RuIIRuIV complex A formulated as [CpRuII-
(µ2-η5:η5-C10H8)RuIVCp(CH3CN)]2ϩ, which was verified by
X-ray analysis.13b The oxidation of A with p-Bq/BF3 at low
temperature probably gives the unstable complex B with the two
higher oxidation state of the RuIV atoms, although it was not
isolated from the solution. Addition of PPh3 to the solution
causes the coordination of PPh3 to the RuIV atoms and the
elimination of the Cp-ring and gives the RuIVRuIV complex C.
Subsequent Zn-reduction of C gives the stable RuIIRuII
complex 2a. On the contrary, the treatment of 1 with PPh3 in
CH3NO2 gave the ring-attacked complex [CpRuII(µ2-η5:η5-
C10H8)RuII(η-C5H4PPh3)]ϩ, the structure of which was con-
firmed by X-ray analysis.12 Thus the formation of an unstable
intermediate complex B in CH3CN at low temperature seems to
be responsible for the formation of complex 2a.
Reactions of 2 with arylthiols and thiolates
The reaction of 2a with some aryl thiols (RC6H4SH, R = H,
CH3 and Cl) in CH2Cl2 gave air-stable and diamagnetic com-
plexes 3a–c, FvRu2(PPh3)2(RC6H4S)2(BF4)2 (R = H, CH3 and
Cl, respectively), as red crystals. The yield of 3a increased on
exposure to the air. Considering the fact that the treatment of
the related Ru() complexes with thiols in the air gave the corre-
sponding Ru() complexes accompanied by air oxidation,14 the
Ru() atoms in 2a may similarly undergo air-oxidation on the
addition of PhSH. The same complexes were also formed by
the oxidation of 2a with p-Bq/BF3 and the subsequent addition
of the thiols. In the 1H NMR spectrum of 3a, the proton signals
of the Fv ligand are found at δ 5.39 and 4.94 at much lower field
compared with those of 2a (δ 4.76 and 4.36), suggesting the
Although a large number of carbonyl Ru2Fv complexes have
been reported, the preparations of various coordination modes
of the Ru2Fv complexes are limited because of the difficulty of
the selective replacement of CO from the complexes by the
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Table 1 Selected bond distances (Å) and angles (Њ)
2b
3a
4a
4c
5a
6b
Ru(1)–Ru(2)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(1)–C(3)
Ru(1)–C(4)
Ru(1)–C(5)
Ru(2)–C(6)
Ru(2)–C(7)
Ru(2)–C(8)
Ru(2)–C(9)
Ru(2)–C(10)
Ru(1)–S(µ2-form)
2.7097(10)
2.189(9)
2.184(8)
2.196(8)
2.265(10)
2.234(8)
2.179(9)
2.191(8)
2.233(8)
2.261(8)
2.6674(8)
2.195(9)
2.203(8)
2.216(8)
2.216(8)
2.232(9)
2.191(7)
2.205(8)
2.230(8)
2.233(8)
2.245(8)
2.355(2) (S(1))
2.361(2) (S(2))
2.391(2) (S(4))
2.358(2) (S(1))
2.350(2) (S(2))
2.401(2) (S(3))
2.6655(7)
2.199(6)
2.204(6)
2.219(6)
2.254(6)
2.232(6)
2.198(5)
2.219(5)
2.234(6)
2.234(6)
2.213(6)
2.342(1) (S(2))
2.335(1) (S(3))
2.365(2) (S(1))
2.342(1) (S(2))
2.335(2) (S(3))
2.355(2) (S(4))
2.7351(8)
2.194(8)
2.190(7)
2.221(8)
2.219(9)
2.223(8)
2.180(8)
2.218(8)
2.231(8)
2.234(8)
2.206(8)
2.349(2) (S(1))
2.363(2) (S(2))
2.6762(10)
2.219(9)
2.220(9)
2.117(6)
2.171(7)
2.113(8)
2.135(7)
2.080(7)
2.201(8)
2.213(10)
2.209(11)
2.161(11)
2.213(14)
2.220(12)
2.234(11)
2.228(14)
2.384(3) (S(1))
2.367(2) (S(2))
2.233(8)
2.353(2) (S(1))
2.365(2) (S(2))
Ru(1)–S(η1-form)
Ru(2)–S(µ2-form)
2.364(2) (S(1))
2.371(2) (S(2))
2.367(2) (S(1))
2.346(2) (S(2))
2.332(3) (S(1))
2.338(3) (S(2))
Ru(2)–S(η1-form)
Ru(1)–L
2.340(2) (L = P(1))
2.063(7) (L = N(1))
2.069(6) (L = N(2))
2.380(2) (L = P(1))
2.398(2) (L = P(1))
2.357(2) (L = P(1))
Ru(2)–L
2.370(3) (L = P(2))
2.394(2) (L = P(2))
Ru(1)–S(µ2)–Ru(2)
S(µ2)–Ru–S(µ2)
70.1(1) (S(1))
69.8(1) (S(2))
75.2(1) (Ru(1))
74.9(1) (Ru(2))
68.9(1) (S(1))
69.0(1) (S(2))
78.0(1) (Ru(1))
78.2(1) (Ru(2))
69.4(1) (S(2))
69.6(1) (S(3))
85.1(1) (Ru(1))
85.1(1) (Ru(2))
70.9(1) (S(1))
71.0(1) (S(2))
77.5(1) (Ru(1))
77.5(1) (Ru(2))
69.1(1) (S(1))
69.3(1) (S(2))
73.0(1) (Ru(1))
74.5(1) (Ru(2))
N(1)–Ru(1)–N(2)
N(1)–Ru(1)–P(1)
N(2)–Ru(1)–P(1)
88.4(3)
98.6(2)
95.2(2)
Scheme 2
formation of a cisoid Ru2Fv complex with an Ru()–Ru()
single bond.
large non-planarity of the Fv ligand (the dihedral angle
between the η5-C5H4 planes of the Fv ligand is 150.8Њ which is
similar to the value reported for Ru2Fv(CO)4 (151.5Њ)1c and
Ru2Fv(CO)3(C2H2) (148.4Њ)1i). The Ru–S(µ2) bond lengths
(2.35–2.37 Å) and the Ru–S(µ2)–Ru bond angles (69.8 and
70.1Њ) are nearly coincident with the values of analogous thiol-
ate-bridged biruthenium complexes15 such as [Ru2Cp*2(SPh)3]ϩ
(2.33–2.36 Å and 66–70Њ, respectively).15d The Ru2S2 core
adopts a butterfly structure and the dihedral angle (core angle)
between the Ru(1)–S(1)–Ru(2) and Ru(1)–S(2)–Ru(2) planes is
96.1Њ, which is smaller than that of the analogous thiolate- and
alkoxide-bridged biruthenium complexes.15,16 It is of note that
the benzene ring of one thiolate ligand is arranged nearly paral-
lel and that of the other is perpendicular to the Fv ligand. This
is in sharp contrast with the complex 4a (vide infra).
To verify this, X-ray diffraction of 3a was carried out. As can
be seen in Fig. 2, the structure of 3a is quite different from that
of 2b. The two Ru atoms lie at the syn positions of the Fv ligand
and the two thiolate ligands coordinate doubly to the Ru
atoms in µ2-form. The cation of 3a is, therefore, formulated as
[(PPh3)RuIII(µ2-η5:η5-C10H8)(µ2-SPh)2RuIII(PPh3)]2ϩ. The mean
Ru(1)–C (2.213 Å) and Ru(2)–C (2.219 Å) distances of the Fv
ligand are significantly longer than that of 2b (2.123 Å), sug-
gesting the presence of the higher oxidation state Ru() atoms
in 3a, and the two unsaturated Ru() atoms require an Ru()–
Ru() bond to achieve an 18-electron configuration. The
Ru()–Ru() distance (2.7097(10) Å) is closer to the value
found for thiolate-bridged diruthenium complexes15 such as
[RuCp*2(SPh)3]ϩ (2.630(1) Å).15d The Ru–Ru bond leads to a
Treatment of 2a with excess aryl thiolates (RC6H4SNa,
D a l t o n T r a n s . , 2 0 0 3 , 6 5 1 – 6 5 8
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perfectly planar. (ii) The Cipso–Cipso bond distance (1.445(13) Å,
C(1)–C(6)) of the Fv ligand in 4a is much longer the corre-
sponding distance (1.38(2) Å) of [Rh2IFv(PMe3)4]I. (iii) The
Ru–Cipso distances (2.195(9) Å for Ru(1)–C(1), 2.191(7) Å for
Ru(2)–C(6)) in 4a are much smaller than the corresponding
distances (2.5114(14) and 2.563(12) Å) in [Rh2IFv(PMe3)4]I.
Consequently, the Fv in 4a is in µ2-η5:η5-C10H8-form rather
than the µ2-η4:η4-C10H8-form and the complex 4a is formulated
as (η1-PhS)RuIII(µ2-η5:η5-C10H8)(µ2-PhS)2RuIII(η1-SPh) and this
is the first example of a cisoid neutral non-carbonyl Fv–Ru
complex. Unlike the case of 3a, the two benzene rings of the
bridging thiolate ligands in 4a are arranged nearly parallel to
the Fv ligand plane in the solid state. This conformation may be
retained in solution because the rotation around the S–Cipso
bond of the bridging thiolate ligand is likely to be restricted by
the presence of the terminal thiolate ligand. As a result, the α
protons in the Fv-ligand are located in the shielding zone of the
benzene ring of the bridging thiolate, resulting in the high field
shifts mentioned above (δ 3.09).
Fig. 2 ORTEP drawing of cation [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-SC6-
H5)2Ru(PPh3)]2ϩ (3a2ϩ), showing 50% probability level of the thermal
ellipsoids and the selective atom-numbering scheme. For clarity all
hydrogen atoms are omitted.
R = H, CH3 and Cl) in CH2Cl2 gave the diamagnetic and neutral
Ru() thiolate complexes 4a–c, FvRu2(RC6H4S)4 (R = H, CH3
and Cl, respectively), in high yield. In the 1H NMR spectrum of
4a, the phenyl protons of PPh3 found in 3a were not observed,
suggesting all the CH3CN and PPh3 ligands of the starting
complex 2a were substituted by the stronger ArSϪ ligands. Two
Fv-proton signals appeared at δ 5.63 and 3.09, implying the
presence of two mirror planes in the Fv-ligand. The fact that
one of them is observed at lower field suggests a structure
similar to 3a for 4a. However, the large chemical shift difference
(∆δ = 2.54 ppm) of the Fv protons compared with that of com-
plex 3a (∆δ = 0.45 ppm) and anomalous higher-field signal at
δ 3.09 may suggest a possibility of an µ2-η4:η4-mode in the Fv
ligand.
The 1H NMR spectrum of 4c was quite different from those
of 4a and 4b, in which four signals at δ 5.75, 5.71, 5.27 and 3.56
were found for the Fv ligand, suggesting lower symmetry
around the Ru atoms. To clarify the structure of 4c, X-ray
analysis has been undertaken. As can be seen in Fig. 4, the
Just recently, the interesting µ2-η4:η4-mode cisoid Rh–Fv
complex, [Rh2IFv(PMe3)4]I, with an Rh–I–Rh bond was
reported,17 in which the Fv protons are found at δ 5.59 and 2.52.
These proton signals are very similar to those found in 4a. To
confirm the structure of 4a, X-ray diffraction was carried out
and the ORTEP view was depicted in Fig. 3. Two thiolate
Fig. 4 ORTEP drawing of (ClC6H4S)Ru(µ2-η5:η5-C10H8)(µ2-SC6H4-
Cl)2Ru(SC6H4Cl) (4c), showing 50% probability level of the thermal
ellipsoids and the selective atom-numbering scheme. For clarity all
hydrogen atoms are omitted.
Fig. 3 ORTEP drawing of (C6H5S)Ru(µ2-η5:η5-C10H8)(µ2-SC6H5)2-
Ru(SC6H5) (4a) showing 50% probability level of the thermal ellipsoids
and the selective atom-numbering scheme. For clarity all hydrogen
atoms are omitted.
fundamental structure of 4c is similar to that of 4a, with two
thiolate ligands coordinated in µ2-form and the other two in
η1-form to the Ru atoms. The Ru–Ru distance (2.6655(7) Å)
and the dihedral angle between the Cp planes (147.6Њ) are nor-
mal. Unlike the case of 4a, typical π-stacking of arenes is found
between the three thiolate benzene rings defined by [C(11)–
C(16)], [C(17)–C(22)] and [C(29)–C(34)], and are roughly per-
pendicular to the Fv ligand. The remaining benzene ring,
[C(23)–C(28)], is nearly parallel to the Fv-ligand. The shortest
C ؒ ؒ ؒ C distance between the benzene rings of the stacked
thiolate ligands is 3.238(8) Å [C(11) ؒ ؒ ؒ C(17)], which is con-
siderably smaller than twice the value (3.40 Å) of the van der
Waals radius of a carbon atom. Thus, these three stacking
thiolate ligands interact spatially each other via pπ–pπ* inter-
actions. This structure of 4c in the solid state may be retained in
the solution, which leads to the four proton signals of the Fv
ligand in 4c, as mentioned above. It is also noteworthy that such
a conformation of the thiolate ligands results in a large core
ligands coordinate to the Ru atoms in µ2-form and the other
two thiolate ligands coordinate in η1-form. The mean Ru–S(µ2)
distance (2.356 Å, which is closer to the value of 3a, (2.363 Å))
is smaller than the value of Ru–S(η1) (2.396 Å). The structure
of the cation of 4a has two mirror planes around the Ru2Fv(µ2-
SPh)2 moiety and this is in sharp contrast with the complex 4c
(vide infra). The Ru–Ru distance (2.6674(8) Å) is shorter than
that of 3a (2.7097(10) Å) and the core angle (99.7Њ) of the Ru2S2
is similar to the value of 3a. The Fv ligand has non-planarity
similarly as found in 3a, the dihedral angle (147.1Њ) between the
two C5H4 planes is similar to that of 3a.
The X-ray results of 4a are in sharp contrast with those
found in the µ2-η4:η4-mode complex, [Rh2IFv(PMe3)4]I, in
three ways. (i) The Fv ligand of complex [Rh2IFv(PMe3)4]I is
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angle (110.8Њ) of the Ru2S2 moiety in 4c, compared with those
of 3a (96.1Њ) and 4a (99.7Њ).
rings defined by [C(29)–C(34)] and [C(41)–C(46)] of PPh3
groups. The three planes are essentially parallel each other
(the dihedral angle of the planes are within ca. 4.0Њ) and per-
pendicular to the Ru–Ru vector. The C(16) ؒ ؒ ؒ C(29) and
C(11) ؒ ؒ ؒ C(41) distances are 3.15(1) and 3.13(1) Å, respect-
ively. Moreover, the three stacking benzene planes with layer
structure are slightly slipped relative to each other. As the
result, the benzene protons of the dithiolate ligand in 5a appear
at much higher field (δ 5.2–5.7). On further addition of sodium
1,2-dithiolate to the solution of 5a, no evidence for the elimin-
ation of the PPh3 ligands of 5a was found. The fact is in sharp
contrast with the reactions of 2a with aryl monothiol and
monothiolate, which gave different products (3 and 4, respect-
ively). These tight π-stacking of the arenes found in 5a may
prevent the elimination of the PPh3 ligand by addition of excess
sodium 1,2-benzenedithiolate.
Reaction of 2 with aryl dithiols and dithiolates
There are only a few studies on benzenedithiolate complexes
compared with those of aryl monothiolate complexes.18–22 The
reaction of 2a with 1,2-benzenedithiol and the related dithiols is
attractive because 1,2-benzenedithiolate has a high chelating
ability for metal atoms. The reaction of 2a with excess 1,2-ben-
zenedithiol or 3,4-toluenedithiol in CH2Cl2 under air gave the
air-oxidized diamagnetic Ru() thiolate complexes [Fv(RuP-
Ph3)2(C6H4S2)](BF4)2 (5a) and [Fv(RuPPh3)2(CH3C6H3S2)]-
(BF4)2 (5b), respectively. The reaction of 2a with the sodium
1,2-benzenedithiol or 3,4-toluenedithiolate gave the same com-
plexes 5a (83%) and 5b (85%), respectively, in high yield. Com-
plex 5a was also prepared by the oxidation of 2a with p-Bq/BF3
and the subsequent addition of sodium 1,2-benzenedithiolate.
In the 1H NMR spectrum of 5a, two proton signals of Fv
ligand are found at δ 5.48 and 5.08, implying the presence of
two mirror planes in the Fv ligand. The most interesting feature
in the 1H NMR spectrum of 5a was found in the proton signals
(δ 5.65 and 5.43) of the dithiolate ligand. Both signals are at
much higher field compared with those of free 1,2-benzenethiol
(δ 7.32) and of reported 1,2-benzenethiolate complexes (6.6–
7.4).18 A similar higher field shift of the thiolate ligand protons
was found in 5b (δ 5.51, 5.46, 5.16). To the best our knowledge,
these higher field shifts are the largest found in 1,2-benzene-
dithiol and related thiol complexes.
Many interesting reactions of the complexes Cp*Ru(SR)n-
RuCp* (R = Et, iPr and tBu; n = 2 and 3) with some alkynes have
been reported,15b,e,h whereas no reaction of 3, 4 and 5 with di-
᎐
phenylacetylene and terminal alkynes (RC᎐CH, R = Ph, C H
᎐
4
9
and C5H11) were found in various conditions, probably because
of the presence of the two coordinatively saturated Ru atoms in
3, 4 and 5.
Reaction of 2 with tert-butylthiolate
Much attention has been paid to the chemistry of binuclear
thiolate Ru–Cp* complexes formulated as Cp*Ru(µ2-SiPr)n-
RuCp* (n = 2 and 3) in which one or two unsaturated Ru atoms
exist potentially. Due to the presence of unsaturated Ru atoms,
the reactions of the complexes with some terminal alkynes gave
a great variety of products.15e,h,i To prepare the similar unsatur-
ated Ru2Fv complexes, the reaction of 2 with an excess of
tBuSH (one of the typical bulky alkylthiols) was carried out,
but no reaction was observed as in the case of [Cp*RuCl2]2 with
tBuSH.15d By contrast, the reaction of 2a with excess tBuSNa in
CH2Cl2 afforded the less stable diamagnetic Ru() complex
FvRu2(tBuS)3(PPh3)BF4 (6a) in 32% yield. In the 1H NMR
spectrum of 6a, four proton signals of the Fv ligand at δ 5.74,
5.32, 4.91 and 4.59 and two proton signals of the tBuSϪ ligand
at δ 1.35 (coordinated), 0.77 (free) are found, suggesting a less
symmetrical geometry around the Fv-ligand and the presence
of an unsaturated Ru atom. The 13C NMR spectrum of 6a also
led to the same conclusions.
In order to rationalize this novel phenomenon, X-ray diffrac-
tion of 5a was carried out. As seen in Fig. 5, the fundamental
To obtain well formed single crystals, the PF6 salt 6b was
obtained by recrystallization of 6a from CH3CN–Et2O in the
presence of NH4PF6. The structure was determined by X-ray
crystallography and the ORTEP plot is shown in Fig. 6. The
Fig.
5
ORTEP drawing of [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-S2C6H4)-
Ru(PPh3)]2ϩ (5a2ϩ), showing 50% probability level of the thermal
ellipsoids and the selective atom-numbering scheme. Top: general view.
Bottom: bottom view. For clarity, all hydrogen atoms are omitted.
structure of 5a is similar to that of 3a, i.e., two sulfur atoms
in the 1,2-benzenedithiolate ligand coordinate to the two Ru
atoms in the µ2-form and the cation is formulated as
[(PPh3)RuIII(µ2-η5:η5-C10H8)(µ2-1,2-C6H4S2)RuIII(PPh3)]2ϩ. The
Ru–Ru distance (2.7351(8) Å), the mean Ru–S(µ2) distance
(2.356 Å), the dihedral angle (150.3Њ) between the η5-C5H4
planes of the Fv ligand and the core angle (100.4Њ) of the Ru2S2
moiety are normal. The typical π-stacking of arenes is found in
the benzene ring planes of the dithiolate and PPh3 ligands.
From the bottom view of Fig. 5, it is seen that the benzene rings
in the dithiolate ligand defined by [C(11)–C(16)] lie between the
Fig. 6 ORTEP drawing of [(PPh3)Ru(µ2-η5:η5-C10H8)(µ2-StBu)2Ru]2ϩ
(6b2ϩ) (StBu)Ϫ, showing 50% probability level of the thermal ellipsoids
and the selective atom-numbering scheme. For clarity all hydrogen
atoms are omitted.
fundamental structure of 6b is quite different from the former
complexes 3–5. Two coordination modes of the Ru atoms are
found; one is the 18-electron configuration around the Ru(1)
atom and the other is the 16-electron configuration around the
Ru(2) atom and the complex 6b is formulated as [(PPh3)-
D a l t o n T r a n s . , 2 0 0 3 , 6 5 1 – 6 5 8
655

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RuIII(µ2-η5:η5-C10H8)(µ2-StBu)2RuIII]2ϩ(BF4Ϫ)(StBuϪ) with two
different coordination geometries of the Ru atoms in the
molecule.
127.5 (d, 9 Hz, m-Ph), 126.8 (s, CN), 89.3 (ipso-C5H4), 75.9
(η-C5H4), 73.8 (η-C5H4) and 1.3 (s, CH3CN); δP (CD3CN) 50.7.
The Ru–Ru (2.6762(10) Å) distances, the Ru–S–Ru (69.1 and
69.3Њ) and S–Ru–S (73.0 and 74.5Њ) angles correspond with
those of reported analogous tert-butylthiolate–Ru complexes16
and the present complexes 3–5. The dihedral angle (147.9Њ)
between the η5-C5H4 planes of the Fv ligand and the core angle
(93.7Њ) of the Ru2S2 moiety are normal. The Ru(1)–S(µ2) dis-
tances (2.384(3), 2.367(2) Å) are somewhat longer than the
values of Ru(2)–S(µ2) (2.332(3) and 2.338(3) Å). Although
the Ru(2) ؒ ؒ ؒ S(3) distance (3.21(1) Å) is too long to form a
bond but it is possible to cause strong interaction between the
atoms. The coordinatively unsaturated Ru(2) atom requires the
[(PPh3)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(ꢀ2-SC6H5)2Ru(PPh3)](BF4)2 (3a).
PhSH (20 mg) was added to a solution of 2a (107 mg, 0.090
mmol) in CH2Cl2 (50 ml). The mixture was stirred for 20 h in air
and then the solvent was evaporated under reduced pressure.
The residue was chromatographed on silica gel by elution with
CH3CN–Et2O (1:1) to give 3a as red crystals (94 mg, 84%), mp
> 210 ЊC (Found: C, 55.61; H, 4.12. C58H48B2F8P2Ru2S2 requires
C, 55.87; H, 3.88%); δH (CDCl3) 7.5–7.2 (36H, m, PPh3 and
SPh), 6.65 (4H, t, SPh), 5.39 (4H, t, η-C5H4) and 4.94 (4H, t,
η-C5H4); δC (CD3CN) 135.2 (ipso-Ph), 134.2 (t, 48 Hz,
o-Ph), 132.3 (br, p-Ph), 129.3 (t, 48 Hz, m-Ph), 131.8 (ipso-SPh),
131.2 (SPh), 130.3 (SPh), 93.6 (η-C5H4), 88.6 (η-C5H4) and 85.4
(ipso-C5H4); δP (CDCl3) 32.6.
t
coordination of the BuS(3)Ϫ anion to satisfy the 18-electron
t
configuration, yet the BuS(3)Ϫ anion remains in an outer
t
sphere coordination site because of the bulkiness of BuSϪ
ligand. Actually, the S(3) ؒ ؒ ؒ C(8) (3.07(2) Å) distance is much
smaller than the sum (3.55 Å) of the van der Waals radius of
the S and C atoms. The low yield of 6 compared with that of
complexes 3–5 must be due to the presence of the unsaturated
Ru atom (some unidentified precipitates were formed during
the reaction of 2 and the thiolate).
[(PPh3)Ru(ꢀ2-ꢁ5ꢁ5-C10H8)(ꢀ2-SC6H4CH3)2Ru(PPh3)](BF4)2
(3b). This complex was prepared in 81% yield using 2a and
p-CH3C6H4SH according to the same method as that described
above, mp > 210 ЊC (Found: C, 56.41; H, 4.42. C60H52B2F8-
P2Ru2S2 requires C, 56.53; H, 4.11%); δH (CDCl3) 7.4–7.0 (34H,
m, PPh3 and SC6H4CH3), 6.51 (4H, d, SC6H4CH3), 5.36 (4H, t,
η-C5H4), 4.83 (4H, t, η-C5H4) and 2.27 (6H, s, CH3); δP (CDCl3)
32.7.
Conclusion
[(PPh3)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(ꢀ2-SC6H4Cl)2Ru(PPh3)](BF4)2
(3c). This complex was prepared in 79% yield using 2a and
p-ClC6H4SH according to the same method as that described
above, mp > 210 ЊC (Found: C, 52.75; H, 3.25. C58H46B2F8Cl2-
P2Ru2S2 requires C, 52.95; H, 3.52%); δH (CDCl3) 7.5–7.1 (34H,
m, PPh3 and SC6H4Cl), 6.51 (4H, d, SC6H4Cl), 5.45 (4H, t,
η-C5H4) and 4.70 (4H, t, η-C5H4); δP (CDCl3) 32.5.
From all the results of the present studies, it can be concluded
that complex 2 is an excellent precursor of a new series of
Fv–diruthenium complexes. The reactions of 2 with some
aryl thiols and thiolates gave the cisoid thiolate-bridged
diruthenium Fv-complexes (3–5) with the direct RuIII–RuIII
bond consisting of two saturated Ru atoms. On the contrary,
the reaction of 2 with sodium tert-butylthiolate gave the thiol-
ate-bridged diruthenium–Fv complex 6 with one coordinatively
unsaturated (16e) Ru atom. The latter is expected to be a
good precursor to synthesize another new series of Ru2–Fv
complexes and investigation along such lines is in progress.
(ꢁ1-C6H5S)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(ꢀ2-SC6H5)2Ru(ꢁ1-SC6H5) (4a).
A solution of 2a (107 mg, 0.090 mmol) in CH2Cl2 (50 ml) was
treated with a solution of PhSNa prepared from sodium
(115 mg, 5 mmol) and PhSH (0.1 g) in MeOH (2 ml). The
mixture was stirred for 20 h and then the solvent was evapor-
ated under reduced pressure. The residue was chromatographed
on silica gel by elution with CH2Cl2 to give 4a (55 mg, 80%) as
dark red crystals, mp 138 ЊC (Found: C, 53.53; H, 3.52.
C34H28Ru2S4 requires C, 53.24; H, 3.68%); δH (CDCl3) 7.98 (2H,
d, SPh), 7.50–6.70 (16H, m, SPh), 6.52 (2H, d, SPh), 5.63 (4H, t,
η-C5H4) and 3.09 (4H, t, η-C5H4).
Experimental
General
All solvents were dried and distilled before use. All chemicals
were standard regent grade and used without further purifi-
cation. 1H-, 13C- and 31P-NMR spectra were recorded on a
Bruker AM-400 instrument using TMS as an internal standard.
31P NMR signals were referred to external 85% H3PO4 as
standard. Abbreviations: s = singlet; d = doublet; t = triplet;
m = multiplet.
(ꢁ1-CH3C6H4S)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(ꢀ2-SC6H4CH3)2Ru(ꢁ1-SC6-
H4CH3) (4b). This complex was prepared in 72% yield using 2a
and p-CH3C6H4SH by the method described above, mp 141 ЊC
(Found: C, 55.35, H, 4.51. C38H36Ru2S4 requires C, 55.45; H,
4.41%); δH (CDCl3) 7.80 (4H, d, SC6H4CH3), 6.98 (4H, d,
SC6H4CH3), 6.59 (4H, d, SC6H4CH3), 6.33 (4H, d, SC6H4CH3),
5.61 (4H, t, η-C5H4) and 3.07 (4H, t, η-C5H4), 2.26 (6H, s,
SC6H4CH3), 2.14 (6H, s, SC6H4CH3).
Syntheses
[(CH3CN)2(PPh3)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)Ru(P-
Ph3)(CH3CN)2](BF4)2 (2a). To a solution of 1 (2.2 g, 3.5 mmol)
and p-benzoquinone (430 mg) in CH3CN (50 ml) and CH2Cl2
(50 ml) was added a solution of BF3ؒEt2O (9 ml) in CH2Cl2
(30 ml) at Ϫ30 ЊC. The solution was stirred for 1 h and then a
solution of PPh3 (4.5 g) in CH2Cl2 (50 ml) was added. The
solution was stirred for 3 h at Ϫ30 ЊC, then warmed to room
temperature followed by stirring for 20 h. To the resulting red–
orange solution, Zn dust (1 g) was added and the mixture was
stirred for 5 h at 40 ЊC, during which Ru() species were fully
reduced and a yellow solution was obtained. After the Zn dust
had been filtered off, the addition of diethyl ether (120 ml)
to the filtrate formed yellow precipitates 2a (3.4 g; 82%), mp
>220 ЊC (decomp.) (Found: C, 54.60; H, 4.43; N, 4.79.
C54H50B2F8N4P2Ru2 requires C, 54.39; H, 4.95; N, 4.66%);
δH (CD3NO2) 7.5–7.3 (30H, m, PPh3), 4.76 (4H, t, η-C5H4), 4.36
(4H, t, η-C5H4) and 2.08 (12H, br, CH3CN); δC (CD3NO2) 132.7
(d, 43 Hz, ipso-Ph), 134.6 (d, 11 Hz, o-Ph), 129.4 (br, p-Ph),
(ꢁ1-ClC6H4S)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(ꢀ2-SC6H4Cl)2Ru(ꢁ1-SC6H4-
Cl) (4c). This complex was prepared in 72% yield using 2a and
p-ClC6H4SH according to the method described above, mp 155
ЊC (Found: C, 45.24; H, 2.72. C34H24Cl4Ru2S4 requires C, 45.14;
H, 2.67%); δH (CDCl3) 7.48 (2H, d, SC6H4Cl), 7.15 (4H, m,
SC6H4Cl), 6.95–6.86 (8H, m, SC6H4Cl), 6.80 (2H, d, SC6H4Cl),
5.75 (2H, t, η-C5H4), 5.71 (2H, t, η-C5H4), 5.27 (2H, t, η-C5H4)
and 3.56 (t, 2H, η-C5H4).
[(PPh3)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(1,2-ꢀ2-C6H4S2)Ru(PPh3)](BF4)2
(5a). This complex was prepared in 83% yield using 2a and
benzene-1,2-dithiol according to the method described for 4a,
mp > 220 ЊC (Found: C, 53.35; H, 3.96. C52H42B2F8P2Ru2S2
requires; C, 53.44; H, 3.62%); δH (CDCl3) 7.5–7.4 (30H, m,
PPh3), 5.65 (2H, virtual quartet, S2C6H4), 5.48 (4H, t, η-C5H4),
D a l t o n T r a n s . , 2 0 0 3 , 6 5 1 – 6 5 8
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5.43 (2H, virtual quartet, S2C6H4) and 5.08 (4H, t, η-C5H4);
δC (CD3CN) 147.5 (t, ipso-1,2-dithiol), 135.2 (br, ipso-Ph), 135.0
(m, o-Ph), 132.9 (br, p-Ph), 129.9 (br, m-Ph), 129.8 (S2C6H4),
127.4 (S2C6H4), 94.0 (η-C5H4), 85.9 (ipso-η-C5H4) and 84.5
(η-C5H4); δP (CDCl3) 45.2.
reflections, R = 0.065 (I > 3σ(I ), 4446 reflections), GOF = 1.137.
The 1H NMR signals of 3aؒCH2Cl2ؒC6H4(OH)2 correspond
with those of 3a except for the signals of C6H4(OH)2 and
CH2Cl2. The atom B(2) was refined isotopically.
4aؒCH2Cl2. Single crystals formulated as 4aؒCH2Cl2 were
grown from a solution of 4a in CH2Cl2 by diffusion of diethyl
ether vapor at Ϫ10 ЊC. Black red needles, C35H30Cl2Ru2S4,
Mr = 851.927, monoclinic, space group P21, a = 10.3140(5),
b = 13.4390(8), c = 12.8140(9) Å, β = 102.500(2)Њ, V = 1734.0(2)
Å3, Z = 2, Dc = 1.632 Mg mϪ3, µ(Mo-Kα) = 1.290 mmϪ1, 6517
measured reflections, R = 0.0495 (I > 2σ(I ), 5763 reflections),
GOF = 1.080. The spectral data indicate the single crystal con-
tains one molecule of CH2Cl2. In the final Fourier map, two Cl
atoms of the CH2Cl2 were located as three positions with
almost same electron densities and the refined as Cl(1), Cl(2)
and Cl(3) with 67% occupancy each.
[(PPh3)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(3,4-ꢀ2-C6H3CH3S2)Ru(PPh3)]-
(BF4)2 (5b). This complex was prepared in 85% yield using 2a
and 3,4-toluenedithiol according to the method described for
4b, mp >220 ЊC (Found: C, 53.65; H, 3.96. C53H44B2F8P2Ru2S2
requires C, 53.82; H, 3.75%); δH (CDCl3) 7.5–7.4 (30H, m,
PPh3), 5.50 (2H, t, η-C5H4), 5.47 (2H, t, η-C5H4), 5.16 (2H, t,
η-C5H4), 5.03 (2H, t, η-C5H4), 5.51 (1H, d, S2C6H3CH3), 5.46
(1H, d, S2C6H3CH3), 5.16 (1H, s, S2C6H3CH3) and 1.49 (3H, s,
S2C6H3CH3); δC (CD3CN) 147.4 (t, ipso-S2C6H3CH3), 144.1
(t, ipso-S2C6H3CH3), 136.9 (t, ipso-S2C6H3CH3), 137.3 (br, ipso-
Ph), 134.6 (d, o-Ph), 132.1 (br, p-Ph), 129.0 (d, m-Ph), 130.8
(S2C6H3CH3), 128.6 (S2C6H3CH3), 127.5 (S2C6H3CH3), 94.0
(η-C5H4), 93.2 (η-C5H4), 85.3 (ipso-η-C5H4), 84.1 (η-C5H4),
83.7 (η-C5H4) and 20.3 (S2C6H3CH3); δP (CDCl3) 45.9.
4c. Single crystals formulated as 4c were grown from a solu-
tion of 4c in CH2Cl2 by diffusion of ether vapor at Ϫ10 ЊC.
Black red needles, C34H24Cl4Ru2S4, Mr = 904.75, triclinic, space
¯
group P1, a = 7.1130(4), b = 13.2430(10), c = 19.248(2) Å,
α = 106.481(4), β = 95.341(6), γ = 99.585(4)Њ, V = 1695.4(3) Å3,
Z = 2, Dc = 1.772 Mg mϪ3, µ(Mo-Kα) = 1.478 mmϪ1, 7631
measured reflections, R = 0.0570 (I > 2σ(I ), 7176 reflections)
GOF = 1.199.
Synthesis of [(PPh3)Ru(ꢀ2-ꢁ5:ꢁ5-C10H8)(ꢀ2-StBu)2Ru](StBu)-
(BF4) (6a). A solution of 2a (107 mg, 0.090 mmol) in CH2Cl2
(50 ml) was treated with the solution of tBuSNa prepared from
Na (100 mg) and tBuSH (20 mg) in MeOH (2 ml). The mixture
was stirred for 20 h and then the solvent was evaporated under
reduced pressure. The residue was chromatographed on silica
gel by elution with CH3CN–Et2O (1:1) to give 6a as red crystals
(27 mg, 32%), mp >210 ЊC (Found: C, 50.84; H, 5.22. C40H50-
BF4PRu2S3 requires C, 50.74; H, 5.32%); δH (CDCl3) 7.5–7.3
(15H, m, PPh3), 5.74 (2H, t, η-C5H4), 5.32 (2H, t, η-C5H4), 4.91
(2H, t, η-C5H4), 4.59 (2H, t, η-C5H4), 1.35 (18H, s, µ-tBuS)
5aؒC6H4(OH)2. Single crystals formulated as 5aؒC6H4(OH)2
were grown from the oxidized solution of 2a with a stoichio-
metric amount of benzoquinone and BF3ؒEt2O in CH2Cl2 and
addition of 1,2-benzenedithiolate at Ϫ10 ЊC for several days.
1
The H NMR signals of 5aؒC6H4(OH)2 correspond with those
of 5a except for the signals of C6H4(OH)2. Orange–red needles,
¯
C58H48B2F8O2P2Ru2S2, Mr = 1278.842, triclinic, space group P1,
a = 10.5000(5), b = 14.0460(7), c = 20.385(1) Å, α = 94.024(2),
β = 97.434(2), γ = 107.514(2)Њ, V = 2824.0(3) Å3, Z = 2, Dc =
1.504 Mg mϪ3, µ(Mo-Kα) = 0.73 mmϪ1, 10295 measured reflec-
tions, R = 0.0811 (I > 2σ(I ), 7168 reflections), GOF = 1.051.
The 1H NMR spectral data indicate the single crystal contains
one molecule of C6H4(OH)2.
t
and 0.77 (9H, s, BuSϪ); δC (CDCl3) 136.8 (m, ipso-Ph), 133.3
(m, o-Ph), 130.0 (br, p-Ph), 127.2 (m, m-Ph), 90.2 (η-C5H4), 85.8
(η-C5H4), 82.2 (η-C5H4), 80.8 (ipso-C5H4), 79.0 (η-C5H4),
48.3 (ipso-µ2-tBuS), 44.6 (ipso-tBuSϪ), 32.1 (µ2-tBuS) and 29.2
(tBuSϪ); δP (CDCl3) 28.4.
6b. Single crystals formulated as 6b were grown from a solu-
tion of 6a in CH3CN containing in large amount of NH4PF6 by
diffusion of diethyl ether vapor at Ϫ10 ЊC for several days. Red
needles, C40H50F6P2Ru2S3, Mr = 1005.108, triclinic, space group
Crystal structure determinations of 2–6
The X-ray diffraction measurements were performed on a
MAC Science Rapid Diffraction Image Processor (DIP 3000)
with graphite-monochromated Mo-Kα radiation and an 18-kW
rotation-anode generator. Reflections were collected using 30
continuous Weissenberg photographs with a Ψ range of 6Њ. The
unit-cell parameters were determined by autoindexing several
images in each data set separately with the DENZO program.
Oscillation Images were processed by using the SCALEPACK
program. The structure was solved with the DIRDIF-PATTY
or SIR method in CRYSTAN-G (software-pack for structure
determination) program system and refined finally by the full-
matrix least squares procedure. The hydrogen atoms, located
from difference Fourier maps or calculation, were isotopically
refined.
¯
P1, a = 10.8940(9), b = 12.492(1), c = 17.162(2) Å, α = 77.769(3),
β = 87.894(4), γ = 72.83(4)Њ, V = 2180.0(4) Å3, Z = 2, Dc = 1.531
Mg mϪ3, µ(Mo-Kα) = 0.96 mmϪ1, 8775 measured reflections,
R = 0.081 (I > 3σ(I ), 4105 reflections), GOF = 1.294.
CCDC reference numbers 191659–191664 for complexes 2b,
3a, 4a, 4c, 5b and 6b, respectively.
See http://www.rsc.org/suppdata/dt/b2/b207928n/ for crystal-
lographic data in CIF or other electronic format.
References
1 (a) R. Boese, M. A. Huffman and K. P. C. Vollhardt, Angew. Chem.,
Int. Ed. Engl., 1991, 30, 1463; (b) J. S. Drage, M. Tilset, K. P. C.
Vollhardt and T. W. Weidman, J. Am. Chem. Soc., 1983, 105, 1675;
(c) J. S. Drage, M. Tilset, K. P. C. Vollhardt and T. W. Weidman,
Organometallics, 1984, 3, 82; (d ) K. P. C. Vollhart and T. W.
Weidman, J. Am. Chem. Soc., 1983, 105, 1675; (e) K. P. C. Vollhart,
J. K. Cammack, A. J. Matzger, A. Bauer, K. B. Capps and C. D.
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and K. P. C. Vollhart, J. Chem. Soc., Chem. Commun., 1996, 1593;
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2 D. Astruc, Acc. Chem. Rev., 1997, 30, 383 and references therein.
3 (a) A. Cano, T. Cuenca, M. Galakhov, G. M. Rodriguez, P. Poyo,
C. J. Cardin and M. A. Convery, J. Organomet. Chem., 1995, 493, 17;
(b) E. Royo, M. Galakhov, P. Royo and T. Cuence, Organometallics,
2000, 19, 3347; (c) E. Royo, P. Royo and T. Cuenca, Organometallics,
2000, 19, 5559; (d ) E. Royo, P. Royo, T. Cuenca and M. Galakhov,
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2b. Single crystals of 2b were grown from a solution of 2a
in the presence of NH4PF6 in CH3CN by diffusion of diethyl
ether vapor at Ϫ10 ЊC for several days. C54H50F12N4P4Ru2, Mr =
¯
1309.034, triclinic, space group P1, a = 9.1510(8), b = 10.180(2),
c = 15.852(2) Å, α = 83.319(6), β = 103.008 (7), γ = 104.474(8)Њ,
V = 1390.3(3) Å3, Z = 1, Dc = 1.563 Mg mϪ3, µ(Mo-Kα) = 0.739
mmϪ1, 6024 measured reflections, R = 0.0892 (I > 2σ(I ), 5731
reflections), GOF = 1.200.
3aؒCH2Cl2ؒC6H4(OH)2. Single crystals formulated as 3aؒ
CH2Cl2ؒC6H4(OH)2 were grown from the oxidized solution of
2a with a stoichiometric amount of benzoquinone and BF3ؒ
Et2O in CH2Cl2 and addition of C6H5SH at Ϫ10 ЊC for several
days. Red needles, C65H56B2Cl2F8O2P2Ru2S2, Mr = 1441.889,
monoclinic, space group P21/c, a = 10.835(1), b = 22.267(4),
c = 25.606(4) Å, β = 100.057(7)Њ, V = 6083.0(2) Å3, Z = 4, Dc
= 1.575 Mg mϪ3, µ(Mo-Kα) = 0.78 mmϪ1, 17358 measured
D a l t o n T r a n s . , 2 0 0 3 , 6 5 1 – 6 5 8
657

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