First star-like oligophenylene molecules containing a dinuclear organometallic core

Article abstract of DOI:10.1002/ejic.200390135

The cationic complexes Ru₂[(p-MeC₆H₄iPr)₂ (p-SC₆H₄Br)₃]⁺ and Rh₂[(C₅Me₅)₂ (p-SC₆H₄Br)₃]⁺ are available in quantitative yields from the reaction of p-HSC₆H₄Br with [Ru(p-MeC₆H₄iPr)Cl₂]₂ and [Rh(C₅Me₅)Cl₂]₂ respectively. These complexes are found to undergo triple Suzuki coupling with oligophenylene boronic acids to give [Ru₂(p-MeC₆H₄iPr)₂ [p-S-(C₆H₄)_n-C₆ H₅}₃]⁺ and [Rh₂(C₅Me₅)₂{p-S- (C₆H₄)n-C₆H₅} ₃]⁺ respectively. The star-like trisbromo complexes are potential precursors for the insertion of dinuclear organometallic entities into the main chain of conjugated molecules. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200390135

SHORT COMMUNICATION
First Star-Like Oligophenylene Molecules Containing a Dinuclear
Organometallic Core
[a]
[a]
[a]
´ ´
´
Frederic Cherioux,* Bruno Therrien, and Georg Süss-Fink
Dedicated to Professeur Bernard Laude on the occasion of his 65th birthday
Keywords: Rhodium / Ruthenium / Oligomerization / Oligophenylene
The cationic complexes Ru2[(p-MeC6H4iPr)2(p-SC6H4Br)3]+
and Rh2[(C5Me5)2(p-SC6H4Br)3]+ are available in quanti-
tative yields from the reaction of p-HSC6H4Br with [Ru(p-
MeC6H4iPr)Cl2]2 and [Rh(C5Me5)Cl2]2 respectively. These
complexes are found to undergo triple Suzuki coupling with
oligophenylene boronic acids to give [Ru2(p-MeC6H4iPr)2{p-
S-(C6H4)n-C6H5}3]+ and [Rh2(C5Me5)2{p-S-(C6H4)n-C6H5}3]+
respectively. The star-like trisbromo complexes are potential
precursors for the insertion of dinuclear organometallic entit-
ies into the main chain of conjugated molecules.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
SC6H4Br)3]ϩ and [Rh2(C5Me5)2(p-SC6H4Br)3]ϩ and the in-
crease of their conjugation length by Suzuki coupling reac-
tions with oligophenylene boronic acids.
During the two past decades there has been a growing
interest in the field of conjugated molecules containing
metal centers because of their electronic, nonlinear optical,
magnetic and catalytic properties,[1Ϫ3] and more recently for
the development of sensors.[4,5] It is quite impossible to be
exhaustive because of the plethora of new compounds syn-
thesized in all these fields of research, but, to the best of
our knowledge, all relevant molecules are built around
mononuclear building blocks coordinated by different types
of organic ligand such as metallocenes, salens, dithiolenes
or ‘‘nitrogen bridges’’ (terpyridines, bipyridines or porphyr-
ins). These types of molecules are the most common in the
literature because of their extraordinary ability to develop
supramolecular structures.[1,6] However, the challenge re-
mains to develop versatile and selective strategies with a
view to creating new molecular designs and new bridging li-
gands.
Results and Discussion
In accordance with our previous studies,[13] the dinuclear
dichloro complexes [Ru(p-MeC6H4iPr)Cl2]2 and [Rh-
(C5Me5)Cl2]2 are found to react in ethanol with p-bromo-
thiophenol to give the cationic complexes [Ru2(p-MeC6H4-
iPr)2(p-SC6H4Br)3]ϩ (1) and [Rh2(C5Me5)2(p-SC6H4Br)3]ϩ
(2), respectively, which can be isolated in quantitative yield
as the chloride salts (Scheme 1).
Star-shaped molecules can lead to a strong enhancement
of the physical properties — such as nonlinear optical sus-
ceptibilities[7,8] or electronic conductivities Ϫ in hyper-
branched conjugated polymers.[9] Moreover, there is a large
interest in conjugated oligomers for their intrinsic physical
properties[10,11] as because they are model compounds for
the study of the corresponding conductive polymers.[12] In
this paper, we report the first example of dinuclear organo- Scheme 1. Synthesis of star-like trisbromo complexes 1 and 2
metallic species in star-like conjugated molecules with sul-
fur connectivities of the type [Ru2(p-MeC6H4iPr)2(p-
Both cations 1 and 2 are unambiguously characterized
1
by their MS, IR, H and 13C NMR spectroscopic data as
[a]
´
ˆ
Institut de Chimie, Universite de Neuchatel,
well as by satisfactory elemental analysis data of the chlor-
ide salts. These cationic complexes are readily soluble as
their chloride salts in alcohols, acetone and chlorinated
ˆ
Avenue de Bellevaux 51, 2007 Neuchatel, Switzerland
Fax: (internat.) ϩ 41-327/182-511
E-mail: frederic.cherioux@unine.ch
Eur. J. Inorg. Chem. 2003, 1043Ϫ1047  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0306Ϫ1043 $ 20.00ϩ.50/0 1043

´
F. Cherioux, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
solvents. Their molecular structures were confirmed by a and the p-bromophenyl groups can be shown by the NMR
single-crystal X-ray structure analysis of [1]Cl and [2]Cl. spectroscopy. An important shielding of the arene (Cp* or
The cations were found to consist of a closed trigonal bipyr- p-MeC6H4iPr) attached to the metal centers is observed in
amid M2S3 framework (M ϭ Ru or Rh), with each ruth- the NMR spectra, whereas a large deshielding of the signals
enium or rhodium atom being coordinated to an η6-Me- of the p-bromophenyl groups is observed in the correspond-
C6H4iPr or an η5-C5Me5 ligand, respectively, and each sul- ing NMR spectra (see Exp. Sect.). This phenomenon is
fur atom carrying a p-bromophenyl group. The molecular larger in the case of ruthenium-based complexes than in the
structures of 1 and 2 are shown in Figure 1.
rhodium derivatives. This is proof of the ICT between the
p-bromophenyl group and the arene moieties through the
sulfur bridges and the metal centers in cations 1 and 2. The
bromo sites at the periphery can lead to the insertion of
original conductive nodes in the main chain of conjugated
oligomers by organometallic cross-coupling Suzuki reac-
tions[14] with appropriate boronic acid derivatives.
Cations 1 and 2 are found to react with boronic acids (a:
phenylboronic acid; b: 3-biphenylboronic acid; c: 1-naph-
thylboronic acid) in ethanol with Pd0(PPh3)4 as catalyst to
give the star-shaped conjugated oligomers 3 and 4, respect-
ively, with yields ranging from 75 to 85% (See Scheme 2).
We observed only the formation of the trisubstituted com-
pounds.
Scheme 2. Synthesis of star-shaped conjugated complexes 3 and 4
Cations 3 and 4 were characterized by their MS and spec-
1
troscopic data (IR, H and 13C NMR) as well as by satis-
factory elemental analysis data of the chloride salts. These
cationic complexes are very soluble in alcohols, acetone and
chlorinated solvents but not in water. The molecular struc-
Figure 1. Molecular structure of [1]Cl and [2]Cl; the chloride ion,
solvent molecules, and H atoms have been omitted for clarity; dis-
placement ellipsoids are drawn at the 50% probability level; selected
˚
bond lengths (A) and angles(°): [1]Cl Ru(1)ϪS(1) 2.392(2),
Ru(1)ϪS(2) 2.4192(19), Ru(1)ϪS(3) 2.385(2), Ru(2)ϪS(1) 2.411(2), ture of 4a was confirmed by a single-crystal X-ray structure
Ru(2)ϪS(2) 2.3989(19), Ru(2)ϪS(3) 2.402(2), Ru(1)ϪRu(2)
3.3532(8); Ru(1)ϪS(1)ϪRu(2) 88.56(7), Ru(1)ϪS(2)ϪRu(2)
88.20(6), Ru(1)ϪS(3)ϪRu(2) 88.92(8); [2]Cl Rh(1)ϪS(1)
2.3882(16), Rh(1)ϪS(2) 2.4145(17), Rh(1)ϪS(3) 2.3937(16),
Rh(2)ϪS(1) 2.4112(17), Rh(2)ϪS(2) 2.3817(15), Rh(2)ϪS(3)
2.4059(16), Rh(1)ϪRh(2) 3.2254(7); Rh(1)ϪS(1)ϪRh(2) 84.45(5),
Rh(1)ϪS(2)ϪRh(2) 84.52(5), Rh(1)ϪS(3)ϪRh(2) 84.44(5)
analysis of the PF6 salt. The cation maintains the closed
trigonal bipyramid M2S3 framework of its precursor 2, as
shown in Figure 2.
Consequently, the insertion of star-shaped dinuclear or-
ganometallic nodes into the main chain of a conjugated
polymer during their growth is possible via Suzuki cross
The bromo-ended star-shaped arrangement adopted by coupling reactions. These cations can be considered as star-
these complexes is very interesting as these compounds rep- shaped conductive reticulating agents for conjugated oligo-
resent conductive organometallic nodes. The intramolecular mers or polymers like 1,3,5-tribromobenzene and its deriv-
charge transfer (ICT) between the organometallic moieties atives[9,15]
1044
Eur. J. Inorg. Chem. 2003, 1043Ϫ1047

Oligophenylene Molecules Containing a Dinuclear Organometallic Core
SHORT COMMUNICATION
under reduced pressure. The oil obtained was purified by column
chromatography (silica gel, dichloromethane/ethanol 5:1; rf close to
0.8). Cations 1 and 2 were isolated in the form of their chloride
salts, after evaporation of the solvent, as red-orange powders in
quantitative yields.
[Ru2(p-Me-C6H4-iPr)2(p-SC6H4Br)3]؉ (1): Yield: 107 mg; quantit-
3
ative. 1H NMR (200 MHz, CDCl3, 21 °C): δ ϭ 0.82 [d, JH,H
ϭ
7.0 Hz, 6 H, (CH3)2CH], 0.92 [d, 3JH,H ϭ 7.0 Hz, 6 H, (CH3)2CH],
1.64 (s, 6 H, CH3), 1.97 (sept, JH,H ϭ 7.0 Hz, 2 H, (CH3)2CH],
3
3
3
5.23 (d, JH,H ϭ 6.2 Hz, 2 H, CH-Ar), 5.26 (d, JH,H ϭ 5.9 Hz, 2
H, CH-Ar), 5.32 (d, 3JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.60 (d, 3JH,Hϭ
3
6.2 Hz, 2 H, CH-Ar), 7.54 (d, JH,H ϭ 8.8 Hz, 6 H, CH-Ar), 7.86
Figure 2. Molecular structure of [4a]PF6; hexafluorophosphate,
solvent molecules, and H atoms have been omitted for clarity; dis-
placement ellipsoids are drawn at the 50% probability level; selected
(d, 3JH,H ϭ 8.8 Hz, 6 H, CH-Ar) ppm. 13C NMR (50 MHz, CDCl3,
21 °C): δ ϭ 18.09 (CH3), 22.12 [(CH3)2CH], 22.94 [(CH3)2CH],
30.00 [(CH3)2CH], 84.12 (Ru-C-Ar), 85.50 (Ru-C-Ar), 85.96 (Ru-
C-Ar), 100.29 (Ru-C-Ar), 108.00 (Ru-C-Ar), 123.01 (C-Br), 132.60
(C-Ar), 134.61 (C-Ar), 137.16 (C-S) ppm. MS (ESI): m/z ϭ 1036
[Mϩ]. C38H40Br3ClRu2S3 (1070.23): calcd. C 42.65, H 3.77; found
C 42.39, H 4.02.
˚
bond lengths (A) and angles(°): Rh(1)ϪS(1) 2.4113(15),
Rh(1)ϪS(2) 2.4006(15), Rh(1)ϪS(3) 2.4064(15), Rh(2)ϪS(1)
2.3835(14), Rh(2)ϪS(2) 2.3840(14), Rh(2)ϪS(3) 2.4121(17),
Rh(1)ϪRh(2)
3.2124(6);
Rh(1)ϪS(1)ϪRh(2)
84.13(5),
Rh(1)ϪS(2)ϪRh(2) 84.35(5), Rh(1)ϪS(3)ϪRh(2) 83.63(5)
[Rh2(C5Me5)2(p-SC6H4Br)3]؉ (2): Yield: 107 mg; quantitative. 1H
NMR (200 MHz, CDCl3, 21 °C): δ ϭ 1.37 (s, 30 H, CH3), 7.49 (d,
3JH,H ϭ 8.4 Hz, 6 H, CH-Ar), 7.66 (d, JH,H ϭ 8.4 Hz, 6 H, CH-
3
Conclusion
Ar) ppm. 13C NMR (50 MHz, CDCl3, 21 °C): δ ϭ 8.99 (CH3),
2
98.51 (d, JRh,C ϭ 6.8 Hz; Rh-C-Ar), 123.74 (C-Br), 131.77 (C-
In conclusion, we report here the first synthesis of star-
shaped dinuclear organometallic entities, based on a closed
trigonal bipyramid M2S3 framework (M ϭ Ru or Rh). We
have demonstrated that these frameworks are conductive
nodes that ensure the electronic connectivity of the p-brom-
ophenyl group and the arene moieties through the three sul-
fur bridges and the two metal centers. Cations 1 and 2 react
with oligophenylene boronic acid derivatives to give ori-
ginal star-shaped dinuclear organometallic complexes pos-
sessing three oligophenylene moieties. The electrochemical
behavior, the electronic and optical properties of these
conjugated star-shaped oligomers, as well as their insertion
into the main chain of conductive polymers, are currently
being investigated.
Ar), 132.31 (C-Ar), 134.88 (C-S) ppm. MS (ESI): m/z: 1040 [Mϩ].
C38H42Br3ClRh2S3 (1075.91): calcd. C 42.30, H 4.20; found C
42.18, H 4.33.
General Method for the Preparation of 3 and 4: The trisbromo di-
nuclear complex [Ru2(p-MeC6H4iPr)2(p-SC6H4Br)3]Cl (107 mg,
0.1 mmol) or [Rh2(C5Me5)2(p-SC6H4Br)3]Cl (108 mg, 0.1 mmol)
and boronic acid derivatives C6H5-B(OH)2 (a; 40 mg, 0.33 mmol),
C12H9-B(OH)2 (b; 65 mg, 0.33 mmol), and C10H7-B(OH)2 (c;
57 mg, 0.33 mmol), were dissolved in technical grade ethanol.
Then, an aqueous solution of Na2CO3 (1 mL, 2 ), and Pd(PPh3)4
catalyst (0.01 mmol, 11 mg) was added. The resulting mixture was
refluxed in ethanol for 48 hours. After cooling to 20 °C, the red
solution was filtered through Celite and the solvent was removed
under reduced pressure. The oil obtained was purified by column
chromatography (silica gel, dichloromethane/ethanol 10:1; rf close
to 0.8). Cations 3 and 4 were isolated in the form of their chloride
salts, after evaporation of the solvent, as red-orange powders.
Experimental Section
[Ru2(p-MeC6H4iPr)2(p-SC6H4C6H5)3]؉ (3a): Yield: 90 mg; 85%. 1H
3
General Remarks: All reactions were carried out under nitrogen, by
using standard Schlenk techniques. Solvents were degassed prior
to use. The dinuclear dichloro complexes [Ru(p-MeC6H4iPr)Cl2]2
and [Rh(C5Me5)Cl2]2 were synthesized by previously described
methods.[16Ϫ18] All other reagents were purchased (Acros) and used
as received. NMR spectra were recorded with a Varian Gemini 200
BB instrument and referenced to the signals of the residual protons
in the deuterated solvents and TMS. The mass spectra were re-
corded at the University of Fribourg (Switzerland) by Prof. Titus
Jenny. Microanalyses were carried out by the Laboratory of Phar-
maceutical Chemistry, University of Geneva (Switzerland).
NMR (200 MHz, CDCl3, 21 °C): δ ϭ 0.81 [d, JH,H ϭ 7.0 Hz, 6
3
H, (CH3)2CH], 0.92 [d, JH,H ϭ 7.0 Hz, 6 H, (CH3)2CH], 1.70 (s,
3
6 H, CH3), 2.03 (sept, JH,H ϭ 7.0 Hz, 2 H, (CH3)2CH], 5.21 (d,
3
3JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.29 (d, JH,H ϭ 5.9 Hz, 2 H, CH-
Ar), 5.33 (d, 3JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.58 (d, 3JH,Hϭ 5.9 Hz,
3
2 H, CH-Ar), 7.40Ϫ7.54 (m, 9 H, CH-Ar), 7.68 (d, 12 H, JH,H
ϭ
8.4 Hz, CH-Ar), 8.05 (d, JH,H ϭ 8.4 Hz, 6 H, CH-Ar) ppm. 13C
3
NMR (50 MHz, CDCl3, 21 °C): 18.14 (CH3), 22.22
δ
ϭ
[(CH3)2CH], 22.90 [(CH3)2CH], 30.90 [(CH3)2CH], 84.14 (Ru-C-
Ar), 85.08 (Ru-C-Ar), 85.58 (Ru-C-Ar), 85.66 (Ru-C-Ar), 100.31
(Ru-C-Ar), 107.55 (Ru-C-Ar), 127.19 (C-Ar), 127.91 (C-Ar), 129.28
(C-Ar), 133.43 (C-Ar), 137.24 (C-Ar), 140.04 (C-Ar), 141.31 (C-S)
ppm. MS (ESI): m/z ϭ 1027 [Mϩ]. C56H55ClRu2S3 (1061.83): calcd.
C 63.34, H 5.22; found C 63.05, H 5.05.
General Method for the Preparation of 1 and 2: The dinuclear
dichloro complex [Ru(p-MeC6H4iPr)Cl2]2 (60 mg, 0.1 mmol) or
[Rh(C5Me5)Cl2]2 (62 mg, 0.1 mmol) was refluxed in technical grade
ethanol (25 mL). When the complex had completely dissolved, a
solution of p-bromothiophenol (95 mg, 0.5 mmol) in 5 mL of eth-
anol was added dropwise to the hot solution. The resulting mixture
was refluxed in ethanol for 3 hours. After cooling to 20 °C, the red
solution was filtered through Celite, and the solvent was removed
[Ru2(p-MeC6H4iPr)2{p-SC6H4(m-C6H4C6H5)}3]؉
(3b):
Yield:
110 mg; 85%. 1H NMR (200 MHz, CDCl3, 21 °C): δ ϭ 0.82 [d,
3
3JH,H ϭ 7.0 Hz, 6 H, (CH3)2CH], 0.93 [d, JH,H ϭ 7.0 Hz, 6 H,
3
(CH3)2CH], 1.71 (s, 6 H, CH3), 2.03 (sept, JH,H ϭ 7.0 Hz, 2 H,
(CH3)2CH], 5.24 (d, 3JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.31 (d, 3JH,H ϭ
Eur. J. Inorg. Chem. 2003, 1043Ϫ1047
1045

´
F. Cherioux, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
3
5.9 Hz, 2 H, CH-Ar), 5.36 (d, JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.60 8018 reflections measured, 5392 unique (Rint ϭ 0.0719) which were
(d, 3JH,Hϭ 5.9 Hz, 2 H, CH-Ar), 7.40Ϫ7.76 (m, 30 H, CH-Ar),
used in all calculations. The final wR (F2) was 0.0827 (all data).
3
7.89 (s, 3 H, CH-Ar), 8.09 (d, JH,H ϭ 8.1 Hz, 6 H, CH-Ar) ppm. [2]Cl·3CHCl3·0.5C6H6: C44H48Br3Cl10Rh2S3, M ϭ 1473.05, mono-
13C NMR (50 MHz, CDCl3, 21 °C): δ ϭ 18.14 (CH3), 22.19
clinic, P21/n (no. 14), a ϭ 14.0257(11), b ϭ 24.8541(13), c ϭ
3
˚
˚
[(CH3)2CH], 22.95 [(CH3)2CH], 30.90 [(CH3)2CH], 84.12 (Ru-C- 15.9642(13) A, β ϭ 92.495(10)°, U ϭ 5559.8(7) A , T ϭ 153 K,
Ar), 85.01 (Ru-C-Ar), 85.55 (Ru-C-Ar), 85.63 (Ru-C-Ar), 100.25 Z ϭ 4, µ(Mo-Kα) ϭ 3.374 mmϪ1, 10607 reflections measured, 8186
(Ru-C-Ar), 107.67 (Ru-C-Ar), 126.94 (C-Ar), 127.56 (C-Ar), 127.85
(C-Ar), 128.04 (C-Ar), 129.17 (C-Ar), 129.76 (C-Ar), 133.52 (C-
unique (Rint ϭ 0.0433) which were used in all calculations. The
final wR (F2) was 0.1567 (all data).
Ar), 137.48 (C-Ar), 140.60 (C-Ar), 141.25 (C-Ar), 142.28 (C-S) [4a]PF6·2C6H6: C68H69F6PRh2S3, M ϭ 1333.20, monoclinic, P21/c
ppm. MS (ESI): m/z ϭ 1255 [Mϩ]. C74H67ClRu2S3 (1290.11): calcd.
C 68.89, H 5.23, found C 68.65, H 5.35.
(no. 14), a ϭ 19.5028(10), b ϭ 15.0341(9), c ϭ 22.5937(14) A, β ϭ
˚
3
˚
96.209(7)°, U ϭ 6585.8(7) A , T ϭ 153 K, Z ϭ 4, µ(Mo-Kα) ϭ
0.675 mmϪ1, 12536 reflections measured, 6576 unique (Rint
ϭ
[Ru2(p-Me-C6H4-iPr)2(p-SC6H4C10H7)3]؉ (3c): Yield: 100 mg; 85%.
0.0845) which were used in all calculations. The final wR (F2) was
0.1191 (all data).
3
1H NMR (200 MHz, CDCl3, 21 °C): δ ϭ 0.92 [d, JH,H ϭ 7.0 Hz,
6 H, (CH3)2CH], 1.05 [d, 3JH,H ϭ 7.0 Hz, 6 H, (CH3)2CH], 1.86 (s,
he data were measured using a Stoe Image Plate Diffraction system
equipped with a ϕ circle, using Mo-Kα graphite monochromated
radiation (λ ϭ 0.71073 A) with ϕ range 0Ϫ180°, increment 1°, 2θ
3
6 H, CH3), 2.13 (sept, JH,H ϭ 7.0 Hz, 2 H, (CH3)2CH], 5.32 (d,
3
3JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.40 (d, JH,H ϭ 5.9 Hz, 2 H, CH-
˚
Ar), 5.44 (d, 3JH,H ϭ 5.9 Hz, 2 H, CH-Ar), 5.71 (d, 3JH,Hϭ 5.9 Hz,
˚
range from 2.0Ϫ26°, DmaxϪDmin ϭ 12.45Ϫ0.81 A. The structures
3
2 H, CH-Ar), 7.51Ϫ7.62 (m, 21 H, CH-Ar), 7.93 (d, JH,H
ϭ
were solved by direct methods using the program SHELXS-97.[19]
The refinement and all further calculations were carried out using
SHELXL-97.[20] The H-atoms were included in calculated positions
and treated as riding atoms using the SHELXL default parameters.
The non-H atoms were refined anisotropically, using weighted full-
matrix least-square on F2.
3
8.1 Hz, 6 H, CH-Ar), 8.14 (d, JH,H ϭ 8.1 Hz, 6 H, CH-Ar) ppm.
13C NMR (50 MHz, CDCl3, 21 °C): δ ϭ 18.29 (CH3), 22.54
[(CH3)2CH], 22.83 [(CH3)2CH], 30.95 [(CH3)2CH], 84.46 (Ru-C-
Ar), 84.73 (Ru-C-Ar), 85.17 (Ru-C-Ar), 85.52 (Ru-C-Ar), 101.03
(Ru-C-Ar), 106.98 (Ru-C-Ar), 125.75 (C-Ar), 126.26 (C-Ar),
126.62 (C-Ar), 127.35 (C-Ar), 128.43 (C-Ar), 128.81 (C-Ar), 131.10
(C-Ar), 131.51 (C-Ar), 132.95 (C-Ar), 134.15 (C-Ar), 137.20 (C-
Ar), 139.22 (C-Ar), 141.24 (C-S) ppm. MS (ESI): m/z ϭ 1177 [Mϩ].
C68H61ClRu2S3 (1212.00): calcd. C 67.39, H 5.07, found C 67.68,
H 4.91.
CCDC-197151 ([1]Cl·CHCl3), CCDC-197152 ([2]Cl·3CHCl3·
0.5C6H6) and CCDC-197153 ([4a]PF6·2C6H6) contain the
supplementary crystallographic data for this paper. 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: (in-
ternat.) ϩ44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
[Rh2(C5Me5)2(p-SC6H4C6H5)3]؉ (4a): Yield: 90 mg; 75%. 1H NMR
(200 MHz, CDCl3, 21 °C): δ ϭ 1.37 (s, 30 H, CH3), 7.41Ϫ7.55 (m,
3
9 H, CH-Ar), 7.65 (d, JH,H ϭ 8.4 Hz, 6 H, 6 H, CH-Ar), 7.71 (d,
3
3JH,H ϭ 8.1 Hz, 6 H, 6 H, CH-Ar), 7.92 (d, JH,H ϭ 8.1 Hz, 6 H,
CH-Ar) ppm. 13C NMR (50 MHz, CDCl3, 21 °C): δ ϭ 9.05 (CH3),
2
98.20 (d, JRh,C ϭ 7.58 Hz, Rh-C-Ar), 127.08 (C-Ar), 127.40 (C-
Acknowledgments
Ar), 128.23 (C-Ar), 129.30 (C-Ar), 131.97 (C-Ar), 134.01 (C-Ar),
139.75 (C-S) ppm. MS (ESI): m/z ϭ 1031 [Mϩ]. C56H57Cl1Rh2S3
(1067.51): calcd. C 63.01, H 5.38, found C 62.76, H 5.52.
Financial support of the Fond National Suisse de la Recherche
Scientifique is gratefully acknowledged. The authors are also in-
debted to the Johnson Mathey Technology Centre for a loan of
[Rh2(C5Me5)2{p-SC6H4(m-C6H4C6H5)}3]؉ (4b): Yield: 97 mg; 75%. ruthenium trichloride hydrate.
1H NMR (200 MHz, CDCl3, 21 °C): δ ϭ 1.44 (s, 30 H, CH3),
7.41Ϫ7.77 (m, 30 H, CH-Ar), 7.89 (s, 3 H, CH-Ar), 7.95 (d,
3JH,H ϭ 8.42 Hz, 6 H, CH-Ar) ppm. 13C NMR (50 MHz, CDCl3,
21 °C): δ ϭ 9.05 (CH3), 98.27 (d, JRh,C ϭ 5.3 Hz, Rh-C-Ar),
126.01 (C-Ar), 127.11 (C-Ar), 127.88 (C-Ar), 128.67 (C-Ar), 129.79
(C-Ar), 132.04 (C-Ar), 134.04 (C-Ar), 140.19 (C-Ar), 141.19 (C-
Ar), 141.69 (C-Ar), 142.39 (C-S) ppm. MS (ESI): m/z ϭ 1259 [Mϩ].
C74H69Cl1Rh2S3 (1295.80): calcd. C 68.59, H 5.37, found C 68.75,
H 5.09.
[1]
J.-M. Lehn, Supramolecular Chemistry, Concepts and Perspect-
2
ives, VCH, Weinheim, 1995.
[2]
[3]
[4]
[5]
[6]
`
´
R. Ziessel, L. Charbonniere, M. Cesario, T. Prange, H. Nieren-
garten, Angew. Chem. Int. Ed. 2002, 41, 975Ϫ979.
´ ´
K. Senechal, O. Maury, H. le Bozec, I. Ledoux, J. Zyss, J. Am.
Chem. Soc. 2002, 124, 4560Ϫ4561.
K. K.-W. Lo, W.-K. Hui, D. Chung-Ming Ng, J. Am. Chem.
Soc. 2002, 124, 9344Ϫ9345.
D. T. MacQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000,
100, 2537Ϫ2574.
U. S. Schubert, C. Eschbaumer, Angew. Chem. Int. Ed. 2002,
41, 2892Ϫ2926. and ref. therein.
[Rh2(C5Me5)2(p-SC6H4C10H7)3]؉ (4c): Yield: 91 mg; 75%. 1H
NMR (200 MHz, CDCl3, 21 °C): δ ϭ 1.47 (s, 30 H, CH3),
3
7.51Ϫ7.65 (m, 21 H, CH-Ar), 7.81 (d, JH,H ϭ 8.1 Hz, 6 H, CH-
3
Ar), 8.01 (d, JH,H ϭ 8.1 Hz, 6 H, CH-Ar) ppm. 13C NMR
[7]
[8]
J. Zyss, I. Ledoux, Chem. Rev. 1994, 94, 77Ϫ105.
C. Dhenault, I. Ledoux, I. D. W. Samuel, M. Bourgault, H. Le
Bozec, Nature 1995, 374, 339Ϫ342.
2
(50 MHz, CDCl3, 21 °C): δ ϭ 9.05 (CH3), 98.13 (d, JRh,C
ϭ
5.5 Hz, Rh-C-Ar), 125.79 (C-Ar), 126.11 (C-Ar), 126.94 (C-Ar),
127.31 (C-Ar), 128.49 (C-Ar), 128.71 (C-Ar), 131.34 (C-Ar), 131.82
(C-Ar), 132.59 (C-Ar), 134.32 (C-Ar), 137.24 (C-Ar), 139.53 (C-
Ar), 142.28 (C-S) ppm. MS (ESI): m/z: 1181 [Mϩ]. C68H63Cl1Rh2S3
(1217.69): calcd. C 67.07, H 5.21, found C 67.39, H 4.97.
[9]
´
F. Cherioux, L. Guyard, Adv. Func. Mater. 2001, 11, 305Ϫ309.
[10]
´
R. Anemian, J.-C. Mulatier, C. Andraud, O. Stephan, J.-C.
Vial, Chem. Commun. 2002, 1608Ϫ1609.
[11]
[12]
[13]
Electronic Materials: The Oligomer Approach (Eds.: K. Müllen
and G. Wegner), Wiley VCH, Weinheim, 1998.
L. L. Miller, Y. Yu, J. Org. Chem. 1995, 60, 6813Ϫ6819 and
references cited therein.
X-ray Crystallographic Study
[1]Cl·CHCl3: C39H41Br3Cl4Ru2S3, M ϭ 1189.57, orthorhombic,
P212121 (no. 19), a ϭ 10.7690(6), b ϭ 15.0037(8), c ϭ 26.6643(16)
´
F. Cherioux, C. M. Thomas, B. Therrien, G. Süss-Fink, Chem.
3
Ϫ1
˚
˚
A, U ϭ 4308.3(4) A , T ϭ 153 K, Z ϭ 4, µ(Mo-Kα) ϭ 3.905 mm
,
Eur. J. 2002, 8, 4377Ϫ4382.
1046
Eur. J. Inorg. Chem. 2003, 1043Ϫ1047

Oligophenylene Molecules Containing a Dinuclear Organometallic Core
SHORT COMMUNICATION
M. A. Bennett, A. K. Smith, J. Chem. Soc., Dalton Trans.
1974, 233Ϫ241.
[14]
[15]
[18]
N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457Ϫ2483.
J. Pang, Y. Tao, S. Freiberg, X.-P. Yang, M. D’Iorio, S. Wang, J.
Mater. Chem. 2002, 12, 206Ϫ212 and references cited therein.
R. A. Zelonka, M. C. Baird, Can. J. Chem. 1972, 50,
3063Ϫ3068.
[19]
[20]
G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467.
G. M. Sheldrick, SHELXL-97. University of Göttingen,
Göttingen, Germany, 1999.
[16]
[17]
J. W. Wang, K. Moseley, P. M. Maitlis, J. Am. Chem. Soc.
1969, 5970Ϫ5977.
Received November 28, 2002
[I02655]
Eur. J. Inorg. Chem. 2003, 1043Ϫ1047
1047