Syntheses and structures of homo- and heterobimetallic, chloro-bridged complexes containing the RuCl3(AsPh3)n fragment (n=1, 2)

Article abstract of DOI:10.1016/j.inoche.2004.03.022

The reaction of [RuCl₃(AsPh₃)₂(MeOH)] with the dimeric complexes [(cod)RhCl]₂, [(ppy)RhCl]₂ (ppy=cyclometalated 2-phenylpyridine), [(cymene)RuCl₂]₂ and [Cp*MCl₂]₂

Full text of DOI:10.1016/j.inoche.2004.03.022

Inorganic Chemistry Communications 7 (2004) 708–712
www.elsevier.com/locate/inoche
Syntheses and structures of homo- and heterobimetallic,
chloro-bridged complexes containing the
RuCl3(AsPh3)n fragment (n ¼ 1, 2) q
*
ꢀ
Sebastien Gauthier, Laurent Quebatte, Rosario Scopelliti, Kay Severin
ꢀ
Institut de Sciences et Ingꢀenierie Chimiques, Ecole Polytechnique Fꢀedꢀerale de Lausanne, CH-1015 Lausanne, Switzerland
Received 3 March 2004; accepted 27 March 2004
Available online 20 April 2004
Abstract
The reaction of [RuCl3(AsPh3)2(MeOH)] with the dimeric complexes [(cod)RhCl]2, [(ppy)RhCl]2 (ppy ¼ cyclometalated 2-phe-
nylpyridine), [(cymene)RuCl2]2 and [Cp*MCl2]2 (M ¼ Rh, Ir) has been investigated. The structure of the resulting products was
shown to depend on the reaction partner. Whereas for the rhodium complexes [(cod)RhCl]2 and [(ppy)RhCl]2, heterobimetallic
compounds with two halogeno-bridges were found, the reactions with the halfsandwich complexes [(cymene)RuCl2]2 and
[Cp*MCl2]2 gave triply bridged products with concomitant formation of mononuclear [(p-ligand)MCl2(AsPh3)] side products. The
new complexes were all characterized by single crystal X-ray analysis.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Heterobimetallic complex; Organometallic complex; Ruthenium; Rhodium; Iridium
Complexes, in which two different metal fragments
are connected by halogeno-bridges, have recently
emerged as a promising new class of catalysts. The
RhIII–RuII complex 1, for example, was shown to dis-
play a very high activity for the ring opening metathesis
polymerization of 1,5-cyclooctadien (Fig. 1) [1,2]. The
structurally related RhIII–RuII complex 2 is able to ef-
ficiently catalyze the oxidation of secondary alcohols
using 2-butanone as the oxidation agent [3] and the RhI–
RuII complex 3 was shown to be a very active and robust
catalyst for the atom transfer radical addition of CCl4 to
olefins [4].
Mixed, halogeno-bridged complexes are accessible by
a variety of synthetic methods [5]. For the synthesis of
compounds with two halogeno-bridges, a metathesis
reaction using the corresponding homobimetallic com-
plexes was found to be the most versatile and easy
method. Reactions of this kind were first described by
the groups of Stone [6] and Masters [7] but more de-
tailed investigations, which demonstrate the potential of
this method, have been published only recently [8,9]. For
the synthesis of mixed complexes with three halogeno-
bridges, several routes were found to give good results.
Initial studies showed that the solvent-stabilized com-
plexes [(CO)3Re(thf)Br]2 [10] and [(PPh3)2ClRu(l-
Cl)3Ru(acetone)(PPh3)2] [3] are well suited starting
materials. These investigations were recently expanded
and numerous other compounds have been identified,
which allow to generate mixed complexes with three
halogeno-bridges in a very efficient way [11]. So far,
investigations in this area have focused on diamagnetic
complexes. In the following, we show that halogeno-
bridged complexes containing a RuIII fragment can be
obtained in reactions of [RuCl3(AsPh3)2(MeOH)] (4)
with dimeric complexes of RuII, RhI, RhIII and IrIII.
The complex [RuCl3(AsPh3)2(MeOH)] (4) can be
synthesized from RuCl3 ꢀ H2O and AsPh3 [12]. It con-
tains a weakly bound methanol ligand which is easily
replaced by other ligands. This is supported by exchange
reactions with acetone [12] and by electrochemical
data which suggest that upon dissolving 4 in CH2Cl2,
q Supplementary data associated with this article can be found, in the
online version, at doi:10.1016/j.inoche.2004.03.022.
* Corresponding author. Tel.: +41-21-6939302; fax: +41-21-6939305.
E-mail address: kay.severin@epfl.ch (K. Severin).
1387-7003/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2004.03.022

S. Gauthier et al. / Inorganic Chemistry Communications 7 (2004) 708–712
709
Cl
Ru
Cl
Rh
Cl
Cl
Cl
Cl
Cl
Cy
Rh
Ru
N
PPh3
PPh3
Cy
N
Cl
1
2
Cy2
Ph
P
Ph
Rh
Cl
P
Cy2
O
Ru
Cl
Cl
N
Ph
O
Ph
Ph
Cl
Ph
N
Cl
Rh
Ph
Ru
Cy2
P
Cl
P
Ph
Cy2
3
Fig. 1. Heterometallic Rh(l-Cl)nRu complexes, which have found
applications as catalysts in metathesis reactions (1), oxidation reac-
tions (2) and atom transfer radical additions (3).
methanol is spontaneously liberated to give the dimer
[Ru2Cl6(AsPh3)4] [13]. In order to obtain heterobime-
tallic Rh–Ru complexes, we have investigated the reac-
tion of 4 with the RhI complex [(cod)RhCl]2 [14] and the
RhIII complex [(ppy)RhCl]2 (ppy ¼ cyclometalated phe-
nylpyridine) [15] (Scheme 1). The reactions were per-
formed in CH2Cl2 and the resulting products 5 and 6
were crystallized from benzene/pentane or from CH2Cl2/
pentane. The new complexes were characterized by ele-
mental analyses and by single crystal X-ray analyses
[16,17]. In both cases, heterobimetallic Rh–Ru com-
plexes were obtained. To the best of our knowledge,
they represent the first structurally characterized com-
plexes with RuIII(l-Cl)2Rh connections.
Fig. 2. ORTEP [19] representation of the molecular structure of 5 in
the crystal. The hydrogen atoms are not shown for clarity. Selected
ꢁ
bond lengths (A) and angles (°): Rh1–Cl1 2.395(4), Rh1–Cl2 2.373(4),
Ru1–Cl1 2.411(4), Ru1–Cl2 2.388(4), Ru1–Cl3 2.328(4), Ru1–Cl4
2.307(4), Ru1–As1 2.4710(18), Ru1–As2 2.4798(18); As1–Ru1–As2
178.93(6).
ꢁ
distance of 3.53 A. The Ru(l-Cl)2Rh unit is slightly bent
with a dihedral angle between the normals of the planes
defined by Ru1, Cl1, Cl2 and Rh1, Cl1, Cl2 of 11.2°.
The overall structure of 5 is similar to that of the com-
plex [(cod)Rh(l-Cl)2Ir(PiPr3)2H2] [18] described by
Werner et al.: as for 5, a (cod)RhI fragment is connected
via two chloro-bridges to an octahedral MIII fragment
with donor ligands in trans configuration.
Complex 6 also consists of a Rh fragment, which is
connected by two chloro-bridges to an octahedral RuIII
fragment. But contrary to what is observed for 5, the
arsine ligands are now in cis position to each other
(Fig. 3). This rearrangement is most likely the result of
the increased steric requirements of the octahedral
(ppy)2Rh fragment, which make a trans geometry en-
For complex 5, a square planar (cod)RhI fragment is
coordinated via two chloro-bridges to an octahedral
RuIII fragment. The two AsPh3 ligands are positioned
trans to each other and are aligned in an almost perfect
linear fashion (Fig. 2). The bond lengths of the two
metals to the bridging chloro-ligands are all very similar
ꢁ
(Rh–Cl1/2 ¼ Ru–Cl1/2 ¼ 2.39 ꢁ 0.02 A) and slightly
longer than what is found for the two terminal chloro-
ꢁ
ligands (Ru–Cl3/4 ¼ 2.32 ꢁ 0.01 A). Significant metal–
ꢁ
ergetically less favorable. With 2.527(4) A and 2.551(4)
metal interactions can be ruled out due to a Rh–Ru
III
ꢁ
A, the Rh –Cl bond lengths of complex 6 are signifi-
cantly longer than what was found for the RhI–Cl bond
lengths of complex 5. As it is expected for a complex
with two AsPh3 ligands in cis position, the octahedral
geometry around the RuIII center is slightly distorted
with As1–Ru1–As2 ¼ 105.24(7)°.
AsPh3
Cl
Cl
Cl
Cl
[(cod)RhCl]2
- 2 MeOH
2
Ru
Rh
H
O
AsPh3
AsPh3
In reactions of 4 with the chloro-bridged halfsand-
wich complex [(cymene)RuCl2]2 [20], a mixture of two
products was obtained (Scheme 2). They show a very
different solubility in acetone and can thus be separated.
The soluble complex was identified by NMR spectros-
copy to be the monomeric [(cymene)RuCl2(AsPh3)]. The
second product was found to be the mixed-valence, tri-
ply bridged complex 7 as evidenced by single crystal X-
ray analysis [17,21]. A reaction of this kind was not
unexpected since it was known that one AsPh3 ligand in
Cl
Ru
5
H3C
2
Cl
Cl
AsPh3
Cl
N
Rh
N
4
Ph3As
Ph3As
Cl
Cl
[(ppy)RhCl]2
- 2 MeOH
2
Ru
Cl
6
Scheme 1. Synthesis of the heterobimetallic Rh–Ru complexes 5 and 6.

710
S. Gauthier et al. / Inorganic Chemistry Communications 7 (2004) 708–712
Fig. 4. ORTEP representation of the molecular structure of 7 in the
crystal. The hydrogen atoms are not shown for clarity. Selected bond
ꢁ
lengths (A) and angles (°): Ru2–Cl1 2.450(4), Ru2–Cl2 2.457(4), Ru2–
Cl3 2.460(4), Ru1–As1 2.418(2), Ru1–Cl1 2.501(4), Ru1–Cl2 2.428(4),
Ru1–Cl3 2.436(4), Ru1–Cl4 2.310(4), Ru1–Cl5 2.302(4); As1–Ru1–Cl1
172.57(11), As1–Ru1–Cl4 95.39(13).
Fig. 3. ORTEP representation of the molecular structure of 6 in the
crystal. The hydrogen atoms are not shown for clarity. Selected bond
ꢁ
lengths (A) and angles (°): Rh1–N1 2.038(13), Rh1–N2 2.013(11),
Rh1–Cl1 2.527(4), Rh1–Cl2 2.551(4), Ru1–Cl1 2.437(4), Ru1–Cl2
2.419(4), Ru1–As1 2.4876(18), Ru1–As2 2.4729(18), Ru1–Cl3 2.315(4),
Ru1–Cl4 2.328(4); N1–Rh1–N2 173.2(5), Cl3–Ru1–Cl4 174.79(14),
As1–Ru1–As2 105.24(7).
complexes with AsR3 ligands have been described [22]
but complex 7 appears to be the first one containing an
arene p-ligand.
Reactions with the dimeric halfsandwich complexes
[Cp*MCl2]2 (M ¼ Rh, Ir) [23] were thought to proceed
in a fashion similar to what was found for [(cym-
ene)RuCl2]2. And indeed, the monomeric complexes
[Cp*MCl2(AsPh3)] were obtained as side products
(Scheme 2). But contrary to what was observed for 7,
the other species containing a Cp*M fragment were not
the expected heterobimetallic complexes [Cp*M(l-
Cl)3RuCl2(AsPh3)] but the isomeric ionic complexes 8
and 9 [24]. This was confirmed for both complexes by a
single crystal X-ray analysis [17,25].
The structural data for the complexes 8 (Fig. 5) and 9
(not shown) are very similar. The complexes contain the
dimeric anion [(AsPh3)Cl2As(l-Cl)3AsCl2(ASPh3)] and
the dimeric cation [Cp*M(l-Cl)3MCp*]. Both, the anion
[26] as well as the cation [27], have been described pre-
viously (although only together with other counter ions)
and the bond length and angles found for 8 and 9 are
within the expected range. At present, we have no ex-
planation of why complex 7 forms a neutral dimer,
whereas an ionic complex is found for 8 and 9. It is
conceivable, however, that the neutral and the isomeric
ionic forms are energetically very similar as it was found
for the mixed, bromo-bridged complex [(CO)3Re(l-
Cl)3Ru(cymene)] [10].
Cl
Cl
[(cymene)RuCl2]
- 2 MeOH
Cl
Cl
7
4
Ru
Ru
+
Ru
Cl
AsPh3
AsPh3
Cl
Cl
Cl
Cl
Cl
Cl
Ru
M
Ru
M
Cl
AsPh3
Cl
Ph3As
Cl
[Cp*MCl2]2
1/2
- 2 MeOH
4
+
M
+
AsPh3
Cl
Cl
Cl
Cl
Cl
8 (M = Rh)
9 (M = Ir)
Scheme 2. Synthesis of the complexes 7–9.
4 can easily be replaced [12]. Furthermore, a similar
ligand transfer has been observed for reactions of
[(cymene)RuCl2]2with ruthenium carbene complexes of
the general formula [RuCl2(PR3)2(CHR0)] [1,2] and for
the reaction with [RuCl2(dppb)(PPh3)] (dppb ¼ 1,4-bis-
diphenylphosphinobutane) [3].
The molecular structure of complex 7 is shown in
Fig. 4. The (cymene)RuII fragment is connected by three
chloro-bridges to the octahedral RuIII fragment con-
taining one AsPh3 ligand. As it was found for 5 and 6,
the Ru–Cl bond lengths to the terminal chloro-ligands
are shorter than the Ru–Cl distances of the bridging
chloro-ligands. A few mixed-valence RuII(l-Cl)3RuIII
In summary, we have described the syntheses and the
structures of five new chloro-bridged complexes con-
taining the RuIIICl3(AsPh3)n (n ¼ 1,2) fragment. The
new compounds were obtained in reactions of
[RuCl3(AsPh3)2(MeOH)] with the dimeric complexes
[(cod)RhCl]2, [(ppy)RhCl]2, [(cymene)RuCl2]2 and
[Cp*MCl2]2 (M ¼ Rh, Ir). The structure and the geom-
etry of the resulting products was shown to depend to a

S. Gauthier et al. / Inorganic Chemistry Communications 7 (2004) 708–712
711
[4] L. Quebatte, R. Scopelliti, K. Severin, Angew. Chem., Int. Ed. 43
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4651–4655;
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24 (1985) 1477–1482.
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[9] (a) M. Ohm, A. Schulz, K. Severin, Eur. J. Inorg. Chem. (2000)
2623–2629;
(b) K. Polborn, K. Severin, J. Chem. soc., Dalton Trans. (1999)
759–764;
Fig. 5. ORTEP representation of the molecular structure of 8 in the
crystal. The hydrogen atoms are not shown for clarity. Selected bond
(c) K. Polborn, K. Severin, Eur. J. Inorg. Chem. (1998) 1187–
1192;
ꢁ
lengths (A) and angles (°): Ru1–As1 2.4212(7), Ru2–As2 2.4161(7),
(d) K. Severin, K. Polborn, W. Beck, Inorg. Chim. Acta 240
(1995) 339–346.
Ru1–Cl4 2.4093(12), Ru1–Cl7 2.3182(12), Ru2–Cl10 2.3060(12), Ru2–
Cl4 2.4222(12), Rh1–Cl1 2.4703(14), Rh1–Cl2 2.4723(13), Rh1–Cl3 2–
4520(12), Ru1ꢄ ꢄ ꢄRu2 3.1367(6), Rh1ꢄ ꢄ ꢄRh2 3.1989(6); As1–Ru1–Cl5
176.15(4); Cl6–Ru1–Cl7 173.35(5).
[10] A.C. da Silva, H. Piotrowski, P. Mayer, K. Polborn, K. Severin, J.
Chem. Soc., Dalton Trans. (2000) 2960–2963.
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(2004) in press.
large extent on the reaction partner. For applications in
homogeneous catalysis, the heterobimetallic Rh–Ru
complexes 5 and 6 appear to be of special interest.
[12] T.A. Stephenson, G. Wilkinson, J. Inorg. Nucl. Chem. 28 (1966)
945–956.
[13] R. Contreras, G.A. Heath, A.J. Lindsay, T.A. Stephenson, J.
Organomet. Chem. 179 (1979) C55–C60.
[14] G. Giordano, R.H. Crabtree, Inorg. Synth. 28 (1990) 88–
90.
Supplementary material
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Soc. 106 (1984) 6647–6653.
An experimental section including detailed synthetic
procedures and elemental analyses is available from the
authors on request. CCDC 232760–CCDC 232764
contains supplementary crystallographic data for this
paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/const/retrieving.html (or from the
Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-
033; or deposit@ccdc.cam.ac.uk).
[16] Crystal data for 5 ꢀ C6H6: C50H48As2Cl4RhRu, Mr ¼ 1144:50,
monoclinic, space group P21=c, a ¼ 18:841ð8Þ, b ¼ 12:562ð4Þ,
ꢁ
c ¼ 20:343ð6Þ A, a ¼ 90°, b ¼ 111:79ð4Þ°, c ¼ 90°, V ¼ 4471ð3Þ
3
A , Z ¼ 4, qcalcd ¼ 1:700 g cmꢂ3, l ¼ 2:450 mmꢂ1, T ¼ 140ð2Þ K,
ꢁ
26,552 reflections collected, 7874 independent reflections,
Rint ¼ 0:1001, Final R indices [I > 2rðIÞ]: R1 ¼ 0:0879, wR2 ¼
0:2391. Crystal data for 6 ꢀ 2 CH2Cl2: C60H50As2Cl8N2RhRu,
Mr ¼ 1436:44, monoclinic, space group P21=c, a ¼ 13:0860ð13Þ,
ꢁ
b ¼ 28:510ð3Þ, c ¼ 16:261ð17Þ A, a ¼ 90°, b ¼ 104:349ð9Þ°,
3
c ¼ 90°, V ¼ 5877:8ð10Þ A , Z ¼ 4, qcalcd ¼ 1:623 gcmꢂ3
,
ꢁ
l ¼ 2:059 mmꢂ1
,
T ¼ 140ð2Þ K, 33,754 reflections collected,
9841 independent reflections, Rint ¼ 0:1409, Final
[I > 2rðIÞ]: R1 ¼ 0:1099, wR2 ¼ 0:2609.
R indices
References
[17] Data reduction and cell refinement was performed with CrysAlis
RED 1.6.9 (Oxford Diffraction Ltd., Abingdon, Oxfordshire,
OX14 1 RL, UK, 2002). Absorption correction was applied to all
data sets using an empirical method. All structures were refined
using the full-matrix least-squares on F2 with all non-H atoms
anisotropically defined. The hydrogen atoms were placed in
calculated positions using the riding model with Uiso ¼ aꢃUeq(C)
(where a is 1.5 for methyl hydrogen atoms and 1.2 for others, C is
the parent carbon atom). Space Group Determination, structure
refinement and geometrical calculations were carried out on all
structures with the SHELXTL software package, release 5.1
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S. Gauthier et al. / Inorganic Chemistry Communications 7 (2004) 708–712
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[25] Crystal data for 8: C56H60As2Cl10Rh2Ru2, Mr ¼ 1645:34, triclinic,
ꢂ
space group P1, a ¼ 10:7154ð6Þ, b ¼ 14:1944ð10Þ, c ¼ 20:0355ð12Þ
ꢁ
[20] M.A. Bennett, T.-N. Huang, T.W. Matheson, A.K. Smith, Inorg.
Synth. 21 (1982) 74–78.
A, a ¼ 91:732ð5Þ°, b ¼ 96:701ð5Þ°, c ¼ 90:966ð5Þ°, V ¼ 3024:5ð3Þ
3
A , Z ¼ 2, qcalcd ¼ 1:807 g cmꢂ3, l ¼ 2:590 mmꢂ1, T ¼ 140ð2Þ K,
ꢁ
[21] Crystal data for 7 ꢀ CHCl3: C29H30AsCl8Ru2, Mr ¼ 939:19,
18,368 reflections collected, 9365 independent reflections,
Rint ¼ 0:0289, Final R indices [I > 2rðIÞ]: R1 ¼ 0:0242, wR2 ¼
0:0497. Crystal data for 9: C56H60As2Cl10Ir2Ru2, Mr ¼ 1823:92,
ꢂ
triclinic, space group P1, a ¼ 9:6173ð13Þ, b ¼ 13:192ð2Þ,
ꢁ
c ¼ 14:665ð2Þ A, a ¼ 115:081ð16Þ°, b ¼ 94:563ð12Þ°, c ¼
3
92:857ð12Þ°, V ¼ 1672:2ð4Þ A , Z ¼ 2, qcalcd ¼ 1:865 g cmꢂ3
,
triclinic, space group P1, a ¼ 10:7713ð7Þ, b ¼ 14:2400ð10Þ, c ¼
ꢁ
ꢂ
l ¼ 2:545 mmꢂ1
,
T ¼ 140ð2Þ K, 10,010 reflections collected,
20:0868ð14Þ A, a ¼ 91:732ð6Þ°, b ¼ 96:698ð6Þ°, c ¼ 90:626ð6Þ°,
ꢁ
3
V ¼ 3058:2ð3Þ A , Z ¼ 2, qcalcd ¼ 1:981 g cmꢂ3, l ¼ 6:368 mmꢂ1
,
ꢁ
5155 independent reflections, Rint ¼ 0:0764, Final
[I > 2rðIÞ]: R1 ¼ 0:0820, wR2 ¼ 0:2249.
R
indices
T ¼ 140ð2Þ K, 17,797 reflections collected, 9434 independent
reflections, Rint ¼ 0:0282, Final R indices [I > 2rðIÞ]: R1 ¼ 0:0290,
wR2 ¼ 0:0776.
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