Subsequent hydride substitution in (arene)trihydridodiruthenium complexes: Synthesis and structure of thiolato-bridged diruthenium cations of the type [H2(arene)2Ru2(p-X-C6H 4-S)]+ and [H(arene)2Ru2(p-X-C 6H4-S)2]+

Article abstract of DOI:10.1002/ejic.200400015

The cationic complexes [HRu₂(η⁶-arene) ₂{μ₂-(p-X-C₆H₄)-S} ₂]⁺ and [H₂Ru₂(η⁶- arene)₂{μ₂-(p-X-C₆H₄)-S}] ⁺ (arene = 1,2,4,5-Me₄C₆H₂ or C ₆Me₆; X = Br and Me) are accessible in good yields from p-X-C₆H₄-SH with [H₃Ru₂(1,2,4,5- Me₄C₆H₂)₂][BF₄] and [H₃Ru₂(C₆Me₆)₂][BF ₄], respectively. The dibromo derivative [HRu₂(C ₆Me₆)₂(p-Br-C₆H₄-S) ₂]⁺ is found to undergo double Suzuki coupling reactions with 3-thiophene boronic acid to give [HRu₂(C₆Me ₆)₂(p-C₄H₃S-C₆H ₄-S)₂]⁺. This dibromo complex is a potential precursor for the insertion of dinuclear hydrido organometaric entities in the main chain of conjugated molecules. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400015

SHORT COMMUNICATION
Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes:
Synthesis and Structure of Thiolato-Bridged Diruthenium Cations of the Type
[H2(arene)2Ru2(p-X؊C6H4؊S)]؉ and [H(arene)2Ru2(p-X؊C6H4؊S)2]؉
[a]
[a,b]
Bruno Therrien,[a] and Georg Süss-Fink[a]
´ ´
´
Mathieu J.-L. Tschan, Frederic Cherioux,*
Dedicated to Professor Jean-Marie Lehn on the occasion of his 65th birthday
Keywords: Ruthenium / Sulfur / Hydrides / Complexes / Cross-coupling
The cationic complexes [HRu2(η6-arene)2{µ2-(p-X−C6H4)−
S}2]+ and [H2Ru2(η6-arene)2{µ2-(p-X−C6H4)−S}]+ (arene
1,2,4,5-Me4C6H2 or C6Me6; X = Br and Me) are accessible in
good yields from p-X−C6H4−SH with [H3Ru2(1,2,4,5-
Me4C6H2)2][BF4] and [H3Ru2(C6Me6)2][BF4], respectively.
The dibromo derivative [HRu2(C6Me6)2(p-Br−C6H4−S)2]+ is ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
3-thiophene boronic acid to give [HRu2(C6Me6)2(p-C4H3S−
C6H4−S)2]+. This dibromo complex is a potential precursor for
the insertion of dinuclear hydrido organometallic entities in
the main chain of conjugated molecules.
=
found to undergo double Suzuki coupling reactions with
Germany, 2004)
Introduction
complexes.[11] The presence of bromo functions at the
periphery of [Ru2(η6-arene)2{µ2-(p-BrϪC6H4)ϪS}3]ϩ and
[Rh2(η5-C5Me5)2{µ2-(p-BrϪC6H4)ϪS}3]ϩ was judiciously
exploited to insert thiophene derivatives by standard Suzuki
cross-coupling reactions.[12] However, despite the successful
synthesis of conjugated oligomers (i.e. coupling with mono-
boronic acids), we were unable to characterize the corre-
sponding polymers (i.e. coupling with diboronic acids). This
can be explained by a large degree of reticulation due to the
presence of three bromine atoms in the starting complexes.
Consequently, the challenge consists of finding new com-
plexes that contain only one or two bromine atoms (instead
of three) at their periphery, therefore allowing a better con-
trol for the synthesis of conjugated polymers.
In this paper, we report the first example of dinuclear
organometallic conjugated molecules in a ‘‘zig-zag’’-like
arrangement with mono- and disulfur connectivities,
[H2Ru2(η6-arene)2{µ2-(p-XϪC6H4)ϪS}]ϩ and [HRu2(η6-
arene)2{µ2-(p-XϪC6H4)ϪS}2]ϩ, respectively, and give one
example of extending their conjugation by Suzuki cross-
coupling reactions with 3-thiophene boronic acid.
The field of π-conjugated molecules and polymers con-
taining metal centers has attracted continuous attention
over the past two decades because of their electronic, mag-
netic, or catalytic properties,[1Ϫ4] and more recently, for the
development of sensors.[5,6] To the best of our knowledge,
except for a very recent work by Kim et al. who synthesized
a dinuclear organomolybdenum sulfide complex,[7] all rel-
evant molecules are built around mononuclear building
blocks that are coordinated with different types of organic
ligands. Therefore, there are still challenges to develop ver-
satile and selective strategies, with the view of creating new
molecular designs and bridging ligands for the formation
of oligomers and polymers which contain metal centers.
In recent studies,[8Ϫ10] we have shown that dinuclear
dichloro complexes [Ru(η6-arene)Cl2]2 and [Rh(η5-C5Me5)-
Cl2]2 react in ethanol with p-bromothiophenol to give the
cationic complexes [Ru2(η6-arene)2{µ2-(p-BrϪC6H4)ϪS}3]ϩ
and [Rh2(η5-C5Me5)2{µ2-(p-BrϪC6H4)ϪS}3]ϩ, respectively,
which could be isolated as the chloride salts in quantitative
yield. We have also synthesized the first star-shaped π-con-
jugated oligomers built around dinuclear organometallic
Results and Discussion
[a]
´
ˆ
Institut de Chimie, Universite de Neuchatel,
Avenue de Bellevaux, 51 2000, Switzerland
Fax: (internat.) ϩ41-327-182-511
In order to overcome the reticulation problem which
arises as a result of the three bromine atoms at the periph-
ery of dinuclear precursors, we first focussed our attention
on two different strategies to synthesize mono- and difunc-
tional dinuclear complexes (see Scheme 1): in route A, dif-
E-mail: frederic.cherioux@unine.ch
[b]
´
Departement LPMO, Institut FEMTO-ST, CNRS UMR 6174,
32 Avenue de l’Observatoire, 25044 Besanc¸on cedex, France
Fax: (internat.) ϩ33-381-853-998
E-mail: frederic.cherioux@lpmo.edu
Eur. J. Inorg. Chem. 2004, 2405Ϫ2411
DOI: 10.1002/ejic.200400015
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´
M. J.-L. Tschan, F. Cherioux, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
ferent para-substituted thiophenols are mixed together,
leading to a mixture of all possible substitution compounds
in a stoichiometric ratio, as observed by NMR (1H and
13C{1H}) and mass spectrometry. In route B, an excess of
the dinuclear dichloro complex is used to favor the forma-
tion of mono- and di-µ2-thiolato complexes.
Scheme 2. Reaction of [H3Ru2(η6-arene)2]ϩ with one equivalent of
para-substituted thiophenol
Scheme 1. Strategies for the synthesis of mono- or difunctional
dinuclear complexes
Unfortunately, the different compounds obtained as a
mixture from route A could not be separated by standard
chromatographic techniques, whereas route B only afforded
tri-µ2-thiolato complexes, despite a strict 1:2 ratio of the re-
agents.
Consequently, we reasoned that strategy B would, in
principle, be the most promising method to synthesize of
difunctional dinuclear complexes; however, the dinuclear di-
chloro complexes [Ru(η6-arene)Cl2]2 were too reactive to
stop at the formation of the di-µ2-thiolato derivatives. In
order to overcome this problem, we used the trihydrido
complexes [H3Ru2(η6-arene)2]ϩ, which are accessible from
the reaction of the dinuclear dichloro complexes [Ru(η6-
arene)Cl2]2 (arene: C6Me6, 1,2,4,5-Me4C6H2) with
Scheme 3. Reaction of [H3Ru2(η6-arene)2]ϩ with two or more
equivalents of para-substituted thiophenol
Surprisingly, if two (or more) equivalents of p-
NaBH4,[13Ϫ15] instead of the dichloro complexes themselves. XϪC6H4ϪSH were used with [H3Ru2(η6-arene)2][BF4], the
The dinuclear trihydrido complex [H3Ru2(C6Me6)2]ϩ was reaction led exclusively to the formation of the cationic
found to react with one equivalent of p-XϪC6H4ϪSH (X ϭ complexes [HRu2(C6Me6)2(p-XϪC6H4ϪS)2]ϩ (2aϪb) and
Me or Br) in ethanol to give a mixture of the cationic com- [HRu2(1,2,4,5-Me4C6H2)2(p-XϪC6H4ϪS)2]ϩ (2cϪd, see
plexes [H2Ru2(C6Me6)2(p-XϪC6H4ϪS)]ϩ (1aϪb) and Scheme 3), and no trace of the mono- or tri-µ2-thiolato
[HRu2(C6Me6)2(p-XϪC6H4ϪS)2]ϩ (2aϪb) in a 3:1 ratio. complexes was detected by mass spectrometry.
These cationic complexes can be isolated in good yields as
Both cations 1 and 2 were unambiguously characterized
the tetrafluoroborate salts. In the case of the durene ana- as the tetrafluoroborate salts (see Exp. Sect.). These ionic
logue [H3Ru2(1,2,4,5-Me4C6H2)2]ϩ, the reaction with one compounds are highly soluble in alcohols, acetone and
equivalent of p-XϪC6H4ϪSH (X ϭ Me or Br) in ethanol chlorinated solvents. The molecular structures of selected
yields the cationic complexes [H2Ru2(1,2,4,5-Me4C6H2)2(p- complexes 1a, 2a, 2c and 2d were confirmed by single-crys-
XϪC6H4ϪS)]ϩ (1cϪd) and [HRu2(1,2,4,5-Me4C6H2)2(p- tal X-ray structure analysis of the tetrafluoroborate salts.
XϪC6H4ϪS)2]ϩ (2cϪd), in a 1:4 ratio (see Scheme 2).
These cationic species consist of a trigonal bipyramidal
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Eur. J. Inorg. Chem. 2004, 2405Ϫ2411

Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes
SHORT COMMUNICATION
H2Ru2S or HRu2S2 core, each ruthenium atom being coor-
dinated to an η6-C6Me6 or an η6-1,2,4,5-Me4C6H2 ligand,
and each sulfur atom carrying a p-substituted phenyl group.
The molecular structures of 1a and 2a are shown in Fig-
ure 1, and those of 2c and 2d are shown in Figure 2.
Figure 2. Molecular structures of [2c][BF4] (top) and [2d][BF4]
(bottom); tetrafluoroborate anions and H atoms have been omitted
for clarity; displacement ellipsoids are drawn at the 35 and 50%
˚
probability level, respectively; selected bond lengths (A) and angles
(°) are listed in Table 1
leading to a strongly distorted structure. Consequently, the
two hydrido ligands are nonequivalent, because one of
them, Ha (see Scheme 2), is closer to the p-XϪC6H4ϪS
moiety than the other (Hb). Moreover, Ha is in the plane of
deshielding of the para-substituted thiophenyl group (see
Figure 1). This phenomenon leads to a large difference in
the chemical shift of Ha (Ϫ12.88 ppm) and Hb
(Ϫ16.75 ppm), as observed in 1H NMR spectrum of 1a. As
Figure 1. Molecular structures of [1a][BF4] (top) and [2a][BF4]
(bottom); tetrafluoroborate anions, solvent molecules and H atoms
have been omitted for clarity; displacement ellipsoids are drawn at
the 25 and 35% probability level, respectively; selected bond lengths
˚
(A) and angles (°) are listed in Table 1
The metal backbone of 1a and 2a consists of two ru- far as complexes 2 are concerned, the chemical shifts as-
thenium atoms, the RuϪRu distances being in accordance signed to the hydrido ligands are found between Ϫ11 and
with a metalϪmetal double bond [1a: RuϪRu ϭ 2.624(2) Ϫ12 ppm. As the molecular structures of 2a, 2c and 2d (see
˚
˚
A] or single bond [2a: RuϪRu ϭ 2.8112(6) A]. The presence Figure 1 and Figure 2) reveal, the hydrido ligand of these
of one or two thiolato bridging ligands forces the complexes is also in the plane of deshielding of the thi-
areneϪRuϪRuϪarene moieties to adopt a distorted ge- ophenyl moiety, leading to chemical shifts similar to those
ometry. The two C6Me6 arene ligands are not parallel to observed for the most deshielded hydrido ligands in com-
each other, and the angles between the C6Me6 planes are plexes 1.
21.2° in 1a and 37.4° in 2a.
The reactivities of the dinuclear trihydrido complexes
The single-crystal X-ray structure analysis of [1a]BF4 ex- [H3Ru2(η6-arene)2]ϩ are completely different from that of
plains the large difference in the chemical shifts observed in the [Ru(η6-arene)Cl2]2 complexes. In the case of the chloro-
1H NMR spectrum of this complex between the two hyd- bridged complexes, only the trisubstituted products are
rido ligands (Ϫ12.88 and Ϫ16.75 ppm), as well as that ob- formed, whereas the hydrido-bridged complexes exclusively
served for the other dihydrido complexes 1bϪd (see Exp. give rise to mono- and dithiolato derivatives. This is prob-
Sect.). The angle defined by the µ2-(p-XϪC6H4)ϪS bridg- ably due to the lower reactivity of the µ2-hydrido ligand,
ing ligand and the ruthenium atoms is close to 110°, thus relative to that of the µ2-chloro ligand, which implies no
Eur. J. Inorg. Chem. 2004, 2405Ϫ2411
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´
M. J.-L. Tschan, F. Cherioux, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
modification of the metalϪmetal bond during the replace-
In order to develop well-defined conjugated polymers
ment with a µ2-thiolato ligand, as is the case for the substi- possessing dinuclear organometallic entities, we investigated
tution of a µ2-hydrido bridge.
the ability of complex 2a (substituted by two bromine atoms
As only the disubstituted complexes [HRu2(η6- at its periphery) to react with boronic acid by a Suzuki
arene)2{µ2-(p-XϪC6H4)ϪS}2]ϩ (2) are accessible from the cross-coupling reaction, as depicted in Scheme 3.
reaction of [H3Ru2(η6-arene)2]ϩ or [H2Ru2(η6-arene)2{µ2-
(p-XϪC6H4)ϪS}2]ϩ (1) with an excess of p-XϪC6H4ϪSH,
the introduction of a third para-substituted thiophenyl
group seems impossible. In fact, the molecular structures of
2a, 2c and 2d show an important constraint on the two
arene ligands due to steric repulsion with the para-substi-
tuted thiophenyl groups already incorporated (see Figure 1
and Figure 2, selected bond lengths and angles are listed in
Table 1), which prevents substitution of the last hydrido li-
gand by a third thiolato ligand. In addition, the steric hin-
Scheme 4. Suzuki cross-coupling reaction of 3-thiophene boronic
acid with dibromo complex 2a
drance provided by the arene moieties also controls the re-
activity of [H3Ru2(η6-arene)2]ϩ with one equivalent of the
Cation 2a was found to react with 3-thiophene boronic
para-substituted thiophenol. In this case, the ratio of com- acid in ethanol in the presence of Pd(PPh3)4 as a catalyst
plexes 1 and 2 formed is reversed by making the arene li- to give the conjugated complex [HRu2(C6Me6)2(p-
gands more bulky: 1:4 for 1,2,4,5-Me4C6H2 in contrast to C4H3SϪC6H4ϪS)2]ϩ (3) with yields ranging from 10 to
3:1 for C6Me6 (see Scheme 1). Similar effects of arene li- 15%. We observed the formation of the difunctionalized
gands have not been observed so far in the case of [Ru(η6- compounds only. Cation 3 was unambiguously charac-
arene)Cl2]2 complexes.[10,11] As a consequence, it can be terized by standard methods (See Experimental Section).
stated that: i) [Ru(η6-arene)Cl2]2 complexes give only This cationic complex, as the tetrafluoroborate salt, is
trisubstituted
compounds
([Ru2(η6-arene)2{µ2-(p- highly soluble in alcohols, acetone and chlorinated solvents.
XϪC6H4)ϪS}3]ϩ), while the lower reactivity of [H3Ru2(η6- The molecular structure of 3 was confirmed by a single-
arene)2]ϩ leads to the mono- and disubstituted compounds, crystal X-ray structure analysis of the BF4 salt: the cation
[HRu2(C6Me6)2(p-XϪC6H4ϪS)2]ϩ and [H2Ru2(C6Me6)2(p- maintains the trigonal-bipyramidal HRu2S2 framework of
XϪC6H4ϪS)]ϩ; ii) the ratio between mono- and disubsti- its precursor, as shown in Figure 3.
tuted complexes can be tuned by the steric hindrance of the
New materials with unique properties should be access-
arene substituents in the starting trihydrido complexes. This ible by this method, because standard organic dibromo re-
can be used for the synthesis of multifunctional complexes agents (for example 2,5-dibromothiophene, 2,7-dibromoflu-
containing the desired number of functionalized ligands at orene etc.) can be replaced by these organometallic entities.
the periphery.
This original approach could lead to the development of
˚
Table 1. Selected bond lengths (A) and angles (°) for [1a][BF4], [2a][BF4], [2c][BF4], [2d][BF4], and [3][BF4]
[1a][BF4]
[2a][BF4]
[2c][BF4]
[2d][BF4]
[3][BF4]
Interatomic distances
Ru(1)ϪS(1)
Ru(1)ϪS(2)
Ru(2)ϪS(1)
Ru(2)ϪS(2)
Ru(1)ϪRu(2)
S(1)ϪC(11)
S(2)ϪC(21)
C(14)ϪBr(1)
C(24)ϪBr(2)
C(14)ϪC(17)
C(24)ϪC(27)
2.420(9)
2.440(8)
2.3642(10)
2.3669(10)
2.3426(10)
2.3744(10)
2.8112(6)
1.787(4)
1.779(4)
1.894(4)
1.904(4)
2.3740(11)
2.3578(12)
2.3724(11)
2.3594(11)
2.7845(5)
1.783(4)
1.789(4)
1.899(5)
1.905(5)
2.3635(8)
2.3676(9)
2.3577(7)
2.3548(7)
2.7963(5)
1.794(3)
2.369(3)
2.340(3)
2.374(3)
2.396(3)
2.7884(12)
1.806(12)
1.785(11)
2.624(2)
2.06(2)
1.789(3)
1.67(2)
1.507(4)
1.514(4)
1.441(15)
1.516(15)
Angles
Ru(1)ϪS(1)ϪRu(2)
Ru(1)ϪS(2)ϪRu(2)
Ru(1)ϪS(1)ϪC(11)
Ru(1)ϪS(2)ϪC(21)
Ru(2)ϪS(1)ϪC(11)
Ru(2)ϪS(2)ϪC(21)
65.35(14)
110.9(7)
112.4(7)
73.35(3)
72.73(3)
113.86(12)
108.17(13)
116.34(12)
109.43(14)
71.84(3)
72.35(3)
112.33(15)
110.48(14)
110.17(14)
111.67(14)
72.64(2)
72.62(2)
108.59(10)
108.12(10)
109.87(9)
117.52(9)
72.01(8)
72.13(9)
111.5(3)
113.9(4)
113.9(4)
117.0(4)
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Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes
SHORT COMMUNICATION
washed with diethyl ether (3 ϫ 20 mL), dissolved in dichlorometh-
ane, and isolated by preparative thin-layer chromatography on sil-
ica (eluent: acetone/hexane, 1:1, followed by acetone/dichlorometh-
ane, 1:50). The purple fraction was recovered to give the product.
[H2Ru2(C6Me6)2(p-Br؊C6H4؊S)][BF4] ([1a][BF4]): Yield: 40%,
26 mg, 32 µmol. Crystals were obtained by diffusion of diethyl
ether in
a
saturated solution of dichloromethane.1H NMR
(200 MHz, [D6]acetone, 21 °C): δ ϭ Ϫ16.69 (d, 2J ϭ 3 Hz, 1 H,
hydride), Ϫ13.07 (d, 2J ϭ 3 Hz, 1 H, hydride), 2.28 (s, 36 H,
3
3
C6(CH3)6], 7.19 (d, J ϭ 8 Hz, 2 H, H-Ar), 7.50 (d, J ϭ 8 Hz, 2
H, H-Ar) ppm. 13C{1H} NMR (50 MHz, [D6]acetone, 21 °C): δ ϭ
17.3 (RuϪCϪCH3), 95.6 (RuϪCϪCH3), 120.8 (CϪBr), 131.2
(CϪH Ar), 135.5 (CϪH Ar), 141.1 (CϪS) ppm. MS (ESI): m/z ϭ
717 [Mϩ ϩ H]. C30H42BBrF4Ru2S (803.57): calcd. C 43.14, H 5.43;
found C 43.60, H 5.71.
Figure 3. Molecular structure of [3][BF4]; the tetrafluoroborate
anion, solvent molecule, and H atoms have been omitted for clarity;
displacement ellipsoids are drawn at the 25% probability level;
˚
selected bond lengths (A) and angles (°) are listed in Table 1
[H2Ru2(C6Me6)2(p-Me؊C6H4؊S)][BF4] ([1b][BF4]): Yield: 43%,
26 mg, 35 µmol. 1H NMR (200 MHz, [D6]acetone, 21 °C): δ ϭ
2
Ϫ16.75 (d, J ϭ 3.4 Hz, 1H, hydride), Ϫ12.88 (d, 2J ϭ 3.4 Hz, 1H.
promising materials based on the ‘‘zig-zag’’ design as a re-
sult of the disulfur connectivities of the type observed in
[HRu2(C6Me6)2(p-BrϪC6H4ϪS)2][BF4].
hydride), 2.26 [s, 36 H, C6(CH3)6], 7.09 (d, 3J ϭ 8.6 Hz, 2 H, H-Ar),
3
7.15 (d, J ϭ 8.6 Hz, 2 H, H-Ar) ppm. 13C{1H} NMR (50 MHz,
[D6]acetone, 21 °C): δ ϭ 17.2 (RuϪCϪCH3), 20.4 (SϪC6H4ϪCH3),
95.4 (RuϪCϪCH3), 129.0 (C-Ar), 133.5 (C-Ar), 137.1 (C-Ar),
137.6 (CϪS) ppm. MS (ESI): m/z
ϭ ϩ H].
652 [Mϩ
Conclusion
C31H45BF4Ru2S (738.7): calcd. C 50.40, H 6.14; found C 50.62,
H 6.25.
In conclusion, we reported the synthesis of dinuclear or-
ganometallic entities, based on trigonal-bipyramidal Preparation of [H2Ru2(1,2,4,5-Me4C6H2)2(p-X؊C6H4؊S)][BF4]:
The dinuclear trihydrido salt [H3Ru2(1,2,4,5-Me4C6H2)2][BF4]
(40 mg, 71 µmol) and p-bromothiophenol (14.55 mg, 77 µmol) or
p-thiocresol (9.56 mg, 77 µmol) were dissolved in degassed techni-
cal grade dichloromethane (60 mL) and heated at 50 °C for 16
hours. After cooling to room temperature, the red solution was
filtered, and the solvent was evaporated to dryness under reduced
pressure. The red solid was washed with diethyl ether (3 ϫ 20 mL),
dissolved in dichloromethane, and isolated by preparative thin-
layer chromatography on silica (eluent: acetone/hexane 1:1, fol-
lowed by acetone/dichloromethane, 1:50). The purple fraction was
HRu2S2 and H2Ru2S frameworks. We demonstrated that it
is possible to control the functionalization (i.e. insertion of
one or two para-substituted thiophenyl ligands) by the use
of dinuclear trihydrido complexes [H3Ru2(η6-arene)2]ϩ. The
dibromo-substituted
derivative
[HRu2(C6Me6)2(p-
BrϪC6H4ϪS)2]ϩ reacts with 3-thiophene boronic acid by
Suzuki cross-couplings to form the conjugated complex
[HRu2(C6Me6)2(p-C4H3SϪC6H4ϪS)2]ϩ. The development
of original and promising conjugated polymers from the di-
nuclear complexes possessing two bromine substituents at recovered to give the product.
their periphery is currently under investigation.
[H2Ru2(1,2,4,5-Me4C6H2)2(p-Br؊C6H4؊S)][BF4] ([1c][BF4]): Yield:
6%, 3.2 mg, 4 µmol. 1H NMR (200 MHz, [D6]acetone, 21 °C): δ ϭ
2
2
Ϫ16.20 (d, J ϭ 2.9 Hz, 1 H, hydride), Ϫ12.38 (d, J ϭ 2.9 Hz, 1
H, hydride), 2.13 (s, 12H, (C6H2(CH3)4], 2.35 (s, 12H,
(C6H2(CH3)4], 5.93 (s, 4H, H-Ar), 7.33 (d, 3J ϭ 8.5 Hz, 2H, H-Ar),
Experimental Section
General Remarks: All reactions were carried out under a nitrogen
atmosphere, by using standard Schlenk techniques, and the solvents
were degassed prior to use. The dinuclear trihydrido complexes
[H3Ru2(η6-arene)2]ϩ (arene: C6Me6, 1,2,4,5-Me4C6H2) were synthe-
sized by previously described methods.[16Ϫ18] All other reagents
were purchased (Fluka, Acros) and used as received. NMR spectra
were recorded on a VarianϪGemini 200 BB instrument and refer-
enced to the signals of the residual protons in the deuterated sol-
vents. The mass spectra were recorded at the University of Fribourg
(Switzerland) by Prof. Titus Jenny. Microanalyses were carried out
by the Laboratory of Pharmaceutical Chemistry, University of
Geneva (Switzerland).
7.45 (d, J ϭ 8.5 Hz, 2H, H-Ar) ppm. MS (ESI): m/z ϭ 661 [Mϩ
3
ϩ H]. C26H34BBrF4Ru2S (747.46): calcd. C 41.78, H 4.58; found C
41.62, H 4.67.
[H2Ru2(1,2,4,5-Me4C6H2)2(p-Me؊C6H4؊S)][BF4]
([1d][BF4]):
Yield: 6%, 3 mg, 4 µmol. 1H NMR (200 MHz, [D6]acetone, 21 °C):
δ ϭ Ϫ16.35 (d, 2J ϭ 3.4 Hz, 1 H, hydride), Ϫ12.25 (d, 2J ϭ 3.4 Hz,
1 H, hydride), 2.08 (s, 12H, C6H4(CH3)4], 2.31 (s, 3 H, Ar-CH3),
2.33 (s, 12H, C6H2(CH3)4], 5.87 (s, 4 H, H-Ar), 7.10 (d, 3J ϭ
7.8 Hz, 2 H, H-Ar), 7.21 (d, 3J ϭ 7.8 Hz, 2 H, H-Ar) ppm. MS
(ESI): m/z ϭ 596 [Mϩ ϩ H]. C27H37BF4Ru2S (682.6): calcd. C
47.51, H 5.46; found C 47.37, H 5.39.
Preparation of [H2Ru2(C6Me6)2(p-X؊C6H4؊S)][BF4]: The di-
nuclear trihydrido salt [H3Ru2(C6Me6)2][BF4] (50 mg, 81 µmol) and
Preparation of [HRu2(C6Me6)2(p-X؊C6H4؊S)2][BF4]: The di-
nuclear trihydrido salt [H3Ru2(C6Me6)2][BF4] (60 mg, 97 µmol) and
p-bromothiophenol (19 mg, 101 µmol) or p-thiocresol (12.5 mg, p-bromothiophenol (37 mg, 196 µmol) or p-thiocresol (24 mg, 196
101 µmol) were dissolved in degassed technical grade ethanol (60 µmol) were dissolved in degassed technical grade ethanol (60 mL)
mL) and heated under reflux for 16 hours. After cooling to room
temperature, the purple solution was filtered, and the solvent was
evaporated to dryness under reduced pressure. The purple solid was
and heated under reflux for 16 hours. After cooling to room tem-
perature, the red solution was filtered, and the solvent was evapo-
rated to dryness under reduced pressure. The red solid obtained
Eur. J. Inorg. Chem. 2004, 2405Ϫ2411
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2409

´
M. J.-L. Tschan, F. Cherioux, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
was washed with diethyl ether (3 ϫ 20 mL), dissolved in dichloro-
methane, and isolated by preparative thin-layer chromatography on
silica (eluent: acetone/hexane 1:1, followed by acetone/dichloro-
[HRu2(1,2,4,5-Me4C6H2)2(p-Br؊C6H4؊S)2][BF4] ([2c][BF4]): Yield:
67%, 45 mg, 48 µmol. Crystals were obtained by diffusion of di-
ethyl ether into a saturated solution of dichloromethane. 1H NMR
methane 1:50). The red fraction was recovered to give the product. (200 MHz, [D6]DMSO, 21 °C): δ ϭ Ϫ11.24 (s, 1H, hydride), 1.72
(s, 12 H, C6H2(CH3)4], 2.25 (s, 12 H, C6H2(CH3)4], 6.01 (s, 4 H,
[HRu2(C6Me6)2(p-Br؊C6H4؊S)2][BF4] ([2a][BF4]): Yield: 67%,
C6H2(CH3)4], 7.6Ϫ7.2 (m, 8 H, H-Ar) ppm. 13C{1H} NMR
64 mg, 65 µmol. Crystals were obtained by diffusion of diethyl
(50 MHz, [D6]DMSO, 21 °C): δ ϭ 17.4 (RuϪCϪCH3), 18.8
(RuϪCϪCH3), 89.7 (RuϪCϪCH3), 99.3 (RuϪCϪCH3), 100.9
(RuϪCϪH), 131.5 (CϪBr), 131.9 (CϪBr), 134.3 (C-Ar), 134.9 (C-
ether in a saturated solution of dichloromethane. 1H NMR
(200 MHz, [D6]acetone, 21 °C): δ ϭ Ϫ11.97 (s, 1H, hydride), 2.22
(s, 36H, C6(CH3)6], 7.6Ϫ7.1 (m, 4 H, H-Ar); 13C{1H} NMR
Ar), 135.9 (C-Ar), 136.5 (CϪS), 139.8 (CϪS) ppm. MS (ESI):
(50 MHz, [D6]acetone, 21 °C): δ ϭ 16.7 (RuϪCϪCH3), 98.1
(RuϪCϪCH3), 121.5 (CϪBr), 131.5 (C-Ar), 135.2 (C-Ar), 137.7
(CϪS) ppm. MS (ESI): m/z ϭ 903 [Mϩ ϩ H]. C36H45BBr2F4Ru2S2
(990.6): calcd. C 45.11, H 4.73; found C 45.52, H 4.81.
m/z ϭ 848 [Mϩ ϩ H]. C32H37BBr2F4Ru2S2 (934.52): calcd. C 41.12,
H 3.99; found C 41.84, H 4.19.
[HRu2(1,2,4,5-Me4C6H2)2(p-Me؊C6H4؊S)2][BF4]
([2d][BF4]):
Yield: 70%, 40 mg, 50 µmol. Crystals were obtained by diffusion
of diethyl ether into a saturated solution of dichloromethane. 1H
NMR (200 MHz, [D6]acetone, 21 °C): δ ϭ Ϫ11.12 (s, 1 H, hydride),
1.85 (s, 12 H, C6H2(CH3)4], 2.28 (s, 3 H, Ar-CH3), 2.33 (s, 3 H,
Ar-CH3), 2.38 (s, 12 H, C6H2(CH3)4], 5.95 (s, 4 H, C6H2(CH3)4],
7.10 (d, 3J ϭ 8.2 Hz, 2 H, H-Ar), 7.11 (d, 3J ϭ 8.2 Hz, 2 H, H-
Ar), 7.29 (d, J ϭ 8.2 Hz, 2H, H-Ar), 7.46 (d, J ϭ 8.2 Hz, 2 H,
H-Ar) ppm. 13C{1H} NMR (50 MHz, [D6]DMSO, 21 °C): δ ϭ 16.6
(RuϪCϪCH3), 17.9 (RuϪCϪCH3), 20.5 (Ar-CH3), 20.6 (Ar-CH3),
89.6 (RuϪCϪCH3), 91.7 (RuϪCϪH), 98.5 (RuϪCϪH), 99.2
(RuϪCϪH), 100.3 (RuϪCϪH), 129.0 (C-Ar), 129.3 (C-Ar), 129.6
(C-Ar), 130.6 (C-Ar), 132.9 (C-Ar), 133.3 (C-Ar), 134.1 (C-Ar),
136.9 (CϪS), 138.2 (CϪS) ppm. MS (ESI): m/z ϭ 848 [Mϩ ϩ H].
C32H37BBr2F4Ru2S2 (934.52): calcd. C 41.12, H 3.99; found C
41.84, H 4.19.
[HRu2(C6Me6)2(p-Me؊C6H4؊S)2][BF4] ([2b][BF4]): Yield: 65%,
54 mg, 63 µmol. 1H NMR (200 MHz, [D6]acetone, 21 °C): δ ϭ
Ϫ11.97 (s, 1 H, hydride), 2.17 (s, 36 H, C6(CH3)6], 2.31 (s, 6 H, Ar-
CH3), 7.4Ϫ7.0 (m, 4 H, H-Ar); 13C{1H} NMR (50 MHz, [D6]ace-
tone, 21 °C): δ ϭ 16.5 (Ar-CH3), 16.8 (RuϪCϪCH3), 97.7
(RuϪCϪH), 129.3 (C-Ar), 133.5 (C-Ar), 137.4 (CϪS) ppm. MS
(ESI): m/z ϭ 774 [Mϩ ϩ H]. C38H51BF4Ru2S2 (860.89): calcd. C
53.02, H 5.97; found C 52.88, H 6.11.
3
3
Preparation of [HRu2(1,2,4,5-Me4C6H2)2(p-X؊C6H4؊S)2][BF4]:
The dinuclear trihydrido salt [H3Ru2(1,2,4,5-Me4C6H2)2][BF4]
(40 mg, 71 µmol) and p-bromothiophenol (30 mg, 160 µmol) or p-
thiocresol (20 mg, 160 µmol) were dissolved in dichloromethane (40
mL) and heated under reflux for 16 hours. After cooling to room
temperature, the red solution was filtered, and the solvent was eva-
porated to dryness under reduced pressure. The red solid was
washed with diethyl ether (3 ϫ 20 mL), dissolved in dichlorometh-
ane, and isolated by preparative thin-layer chromatography on sil-
Preparation
of
[HRu2(C6Me6)2(p-C4H3S؊C6H4؊S)2][BF4]
([3][BF4]): The dinuclear hydrido salt [HRu2(C6Me6)2(p-
ica (eluent: acetone/hexane, 1:1, followed by acetone/dichlorometh- SϪC6H4ϪBr)2][BF4] (50 mg, 56 µmol) and 3-thiophene boronic
ane, 1:50). The red fraction was recovered to give the product. acid (20.5 mg, 160 µmol) were dissolved in distilled ethanol
Table 2. Crystallographic and selected experimental data of [1a][BF4], [2a][BF4], [2c][BF4], [2d][BF4], and [3][BF4]
[1a][BF4]·C6H6 [2a][BF4]·CO(CH3)2 [2c][BF4] [2d][BF4]
C36H48BBrF4Ru2S C39H51BBr2F4ORu2S2 C32H37BBr2F4Ru2S2 C34H43BF4Ru2S2
[3][BF4]·CH2Cl2
Chemical formula
Molecular mass
Crystal system
Space group
C45H53BCl2F4Ru2S4
1081.96
881.66
1048.69
triclinic
934.51
monoclinic
P21/n
804.75
triclinic
monoclinic
Cc
triclinc
¯
P1
¯
P1
¯
P1
Color and shape
Crystal size
red plate
red rod
red block
red block
orange plate
0.40 ϫ 0.08 ϫ 0.04 0.28 ϫ 0.08 ϫ 0.08
0.25 ϫ 0.25 ϫ 0.15 0.32 ϫ 0.26 ϫ 0.24 0.48 ϫ 0.25 ϫ 0.05
˚
a (A)
16.144(1)
15.021(1)
15.856(1)
90
111.400(9)
90
11.906(1)
13.600(1)
14.603(1)
72.62(1)
81.35(1)
84.41(1)
2227.3(4)
2
11.3006(6)
16.872(1)
18.383(1)
90
90.700(7)
90
11.775(2)
11.796(1)
12.374(2)
93.00(2)
94.01(1)
101.19(2)
1678.1(4)
2
10.731(1)
14.166(2)
16.975(3)
87.39(2)
73.87(1)
70.03(1)
2326.1(6)
2
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
3
˚
V (A )
Z
3580.1(6)
4
3504.5(4)
4
T (K)
153(2)
1.636
2.063
153(2)
1.564
2.610
293(2)
1.771
3.304
153(2)
1.593
1.070
153(2)
1.545
0.991
Dc (g·cmϪ3
)
µ (mmϪ1
)
Scan range (°)
Unique reflections
3.84 Ͻ 2θ Ͻ 52.88 4.26 Ͻ 2θ Ͻ 51.92
4.20 Ͻ 2θ Ͻ 51.90 4.48 Ͻ 2θ Ͻ 52.16 4.06 Ͻ 2θ Ͻ 51.90
6537
8111
6816
6163
8373
Reflections used [I Ͼ 2σ(I)] 3505
Rint 0.0832
Final R indices[I Ͼ 2σ(I)] 0.1203, wR2 0.3025 0.0327, wR2 0.0769
5997
0.0294
4443
0.0528
4834
0.0337
2936
0.1198
0.0339, wR2 0.0723 0.0264, wR2 0.0626 0.0704, wR2 0.1496
0.0633, wR2 0.0779 0.0376, wR2 0.0666 0.1725, wR2 0.1726
R indices (all data)
0.1878, wR2 0.3499 0.0501, wR2 0.0846
Goodness-of-fit
Max, Min ∆ρ/e (A
1.089
4.264, -2.093
0.918
1.079, Ϫ0.870
0.857
1.007, Ϫ0.606
0.939
0.495, Ϫ1.082
0.735
0.773, Ϫ0.651
Ϫ3
˚
)
2410
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2405Ϫ2411

Subsequent Hydride Substitution in (Arene)trihydridodiruthenium Complexes
(15 mL). Sodium carbonate (17 mg, 160 µmol) and tetrakis(tri- debted to the Johnson Mathey Technology Centre for a loan of
SHORT COMMUNICATION
phenylphosphane)palladium (12 mg, 16 µmol) were then added to ruthenium trichloride hydrate.
the solution, which was heated under reflux for four days. After
cooling to room temperature, the red-brown solution was filtered,
[1]
J.-M. Lehn, Supramolecular Chemistry, Concepts and Perspec-
and the solvent was evaporated to dryness under reduced pressure.
The red solid was dissolved in dichloromethane and purified by
preparative thin-layer chromatography on silica (eluent: acetone/
hexane, 1:1, acetone/dichloromethane, 1:50). The red fraction con-
taining the desired product was collected. Yield: 14%, 8 mg, 8
µmol. Crystals were obtained by diffusion of diethyl ether into a
saturated solution of dichloromethane. The MS (ESI) spectra
shows the molecular peak [Mϩ ϩ H] m/z ϭ 910 and two other
peaks corresponding to the loss of one and two thienyl groups
tives, VCH, Weinheim, 1995.
[2]
[3]
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´
R. Ziessel, L. Charbonniere, M. Cesario, T. Prange, H. Nieren-
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K. Senechal, O. Maury, H. le Bozec, I. Ledoux, J. Zyss, J. Am.
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U. S. Schubert, C. Eschbaumer, Angew. Chem. Int. Ed. 2002,
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100, 2537Ϫ2574.
1
(m/z ϭ 827, m/z ϭ 744). H NMR (200 MHz, [D6]acetone, 21 °C):
[7]
δ ϭ Ϫ11.89 (s, 1 H, hydride), 2.23 [s, 36 H, C6(CH3)6], 7.93Ϫ7.24
(m, 14 H, SϪC6H4ϪC4H3S) ppm. for C44H51BF4Ru2S4 (997.1):
calcd. C 53.00, H 5.16; found C 49.87, H 5.19.
D. H. Kim, J.-H. Kim, T. H. Kim, D. M. Kang, Y. H. Kim,
Y.-B. Shim, S. C. Shin, Chem. Mater. 2003, 15, 825Ϫ827.
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F. Cherioux, C. M. Thomas, B. Therrien, G. Süss-Fink, Chem.
Eur. J. 2002, 8, 4377Ϫ4382.
[9]
X-ray Crystallographic Study: The data were measured on a Stoe
Image Plate Diffraction system equipped with a ϕ circle, using Mo-
´
F. Cherioux, C. M. Thomas, T. Monnier, G. Süss-Fink, Poly-
hedron 2003, 22, 543Ϫ548.
[10]
[11]
˚
´
F. Cherioux, B. Therrien, G. Süss-Fink, Inorg. Chim. Acta
Kα graphite-monochromated radiation (λ ϭ 0.71073 A) with ϕ
2004, 357, 834Ϫ838.
range 0Ϫ200°, increment ranging from 1.0Ϫ1.8°, 2θ range from
´
F. Cherioux, B. Therrien, G. Süss-Fink, Eur. J. Inorg. Chem.
˚
2.0Ϫ26°, DmaxϪDmin ϭ 12.45Ϫ0.81 A. The structures were solved
2003, 1043Ϫ1047.
by direct methods with the program SHELXS-97.[19] The refine-
ment and all further calculations were carried out using SHELXL-
97.[20] The H-atoms were included in calculated positions and
treated as riding atoms with the SHELXL default parameters. The
non-H atoms were refined anisotropically, using weighted full-ma-
trix least-square on F2. Figures were drawn with ORTEP.[21] All
crystallographic data are collected in Table 2. CCDC-220959 for
[1a][BF4], -220962 for [2a][BF4], -220961 for [2c][BF4], -220960 for
[2d][BF4], and -220963 for [3][BF4] contain the supplementary crys-
tallographic data. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk]
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M. Jahncke, G. Meister, G. Rheinwald, H. Stoeckli-Evans, G.
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in press.
R. A. Zelonka, M. C. Baird, Can. J. Chem. 1972, 50,
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[19]
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G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467.
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[21]
L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
Acknowledgments
Financial support of the Fond National Suisse de la Recherche
Scientifique is gratefully acknowledged. The authors are also in-
Received January 9, 2004
Early View Article
Published Online May 13, 2004
Eur. J. Inorg. Chem. 2004, 2405Ϫ2411
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2411