New dinuclear face- and edge-sharing bioctahedral ruthenium compounds containing 1,2-bis(diphenylphosphanyloxy)ethane

Article abstract of DOI:10.1002/ejic.200600183

The bidentate diphosphinite ligand 1,2-bis(diphenylphosphanyloxy)ethane (L), Ph₂P-O-(CH₂)₂-O-PPh₂, can be sequentially incorporated into a series of dinuclear chloro-bridged ruthenium compounds using [RuCl₂(DMSO)₄] as a precursor to give the new bioctahedral compounds [Ru₂(μ-Cl)₃(DMSO) ₃Cl(η²-L)] (1), [Ru₂(μ-Cl) ₃(DMSO)Cl(η²-L)₂] (2) and [Ru ₂Cl₂(η²-L)₂{η¹- L(O)}₂(μ-Cl)₂] (3). Compound 3 contains two partially oxidised diphosphinite ligands that act in a monodentate manner. These compounds can also be obtained by direct reaction of [RuCl₂(DMSO)₄] with the appropriate stoichiometric amount of L but in the case of 3 (in which prolonged heating is necessary) the reaction affords two mononuclear compounds [RuCl₂(η²-L)(Ph₂POPPh₂)] (7) and [RuCl(CO)(η²-L)(Ph₂POCH₂)] (8), with ligand fragments coordinated to the metal probably originating in metal-mediated disruptions of L. Reaction of 2 with the monodentate ligands PPh _3-n(OEt)_n (n = 1-3) (L′) affords the dinuclear doubly chloro-bridged compound [Ru₂(μ-Cl)₂Cl ₂(η²-L)₂(L′)₂] (4), the dinuclear triply chloro-bridged compound [{Ru(η²-L)(L′)} ₂-(μ-Cl)₃]Cl (5) and the mononuclear compound [RuCl₂(η²-L)(L′)₂] (6). The solid-state structures of 2 (transoid isomer), 5 (transoid isomer), 6, 7 and 8 are reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200600183

FULL PAPER
DOI: 10.1002/ejic.200600183
New Dinuclear Face- and Edge-Sharing Bioctahedral Ruthenium Compounds
Containing 1,2-Bis(diphenylphosphanyloxy)ethane
Jorge Bravo,*[a] Jesús Castro,[a] Soledad García-Fontán,*[a]
M. Carmen Rodríguez-Martínez,[a] and Pilar Rodríguez-Seoane[a]
Keywords: Ruthenium / P ligands / Chelates / Bimetallic complexes
The bidentate diphosphinite ligand 1,2-bis(diphenylphos-
phanyloxy)ethane (L), Ph2P–O–(CH2)2–O–PPh2, can be se- and [RuCl(CO)(η2-L)(Ph2POCH2)] (8), with ligand fragments
quentially incorporated into a series of dinuclear chloro- coordinated to the metal probably originating in metal-medi-
bridged ruthenium compounds using [RuCl2(DMSO)4] as a ated disruptions of L. Reaction of 2 with the monodentate
two mononuclear compounds [RuCl2(η2-L)(Ph2POPPh2)] (7)
precursor to give the new bioctahedral compounds [Ru2(µ-
ligands PPh3 – n(OEt)n (n = 1–3) (LЈ) affords the dinuclear dou-
Cl)3(DMSO)3Cl(η2-L)] (1), [Ru2(µ-Cl)3(DMSO)Cl(η2-L)2] (2)
bly chloro-bridged compound [Ru2(µ-Cl)2Cl2(η2-L)2(LЈ)2] (4),
and [Ru2Cl2(η2-L)2{η1-L(O)}2(µ-Cl)2] (3). Compound 3 con- the dinuclear triply chloro-bridged compound [{Ru(η2-L)(LЈ)}2-
tains two partially oxidised diphosphinite ligands that act in
a monodentate manner. These compounds can also be ob-
tained by direct reaction of [RuCl2(DMSO)4] with the appro-
priate stoichiometric amount of L but in the case of 3 (in
which prolonged heating is necessary) the reaction affords
(µ-Cl)3]Cl (5) and the mononuclear compound [RuCl2(η2-L)-
(LЈ)2] (6). The solid-state structures of 2 (transoid isomer), 5
(transoid isomer), 6, 7 and 8 are reported.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
tween the metal-containing precursor and the ligand was
varied.
Introduction
Ruthenium complexes continue to attract attention be-
cause they can be used in a range of applications in many
different fields including catalytic processes[1] and bioinor-
ganic processes.[2] Moreover, the discovery of the anticancer
activity of [RuCl2(DMSO)4] has increased interest in the
properties of new Ru–DMSO complexes.[3] A number of
chelating diphosphines have been used to stabilise transi-
tion-metal complexes but, surprisingly, studies on analo-
gous diphosphinites are rare, although some such com-
pounds have proved to be efficient catalysts.[4] Furthermore,
the presence of halogeno bridges between the metal centres
provides higher reactivity, thus enhancing their possibilities
for successful use as new catalysts.[5]
We report here the results obtained in the reaction be-
tween [RuCl2(DMSO)4] and 1,2-bis(diphenylphosphanyl-
oxy)ethane (L) to yield a range of new mono- and dinu-
clear ruthenium complexes (Scheme 1). It is worth men-
tioning that, in contrast with the behaviour observed for
other diphosphinite ligands,[6] it was possible to obtain dif-
ferent products when the stoichiometric relationship be-
Results and Discussion
Reaction of [RuCl2(DMSO)4] with L – Preparation of
[Ru2(µ-Cl)3(DMSO)3Cl(L)] (1)
Reaction of [RuCl2(DMSO)4] with 1,2-bis(diphenylphos-
phanyloxy)ethane (L) in a 2:1 molar ratio in refluxing tolu-
ene for 1/2 h gave a yellow solid. The analytical data for
this compound are consistent with the empirical formula
Ru2LCl4(DMSO)3. The IR spectrum shows a strong band
at 1093 cm–1, which is consistent with the presence of the
η1-S (DMSO) ligands.[7] The 31P{1H} NMR spectrum in
CDCl3 shows a singlet at δ = 158.2 ppm, indicating the
magnetic equivalence of the two phosphorus atoms of the
1
bidentate ligand L. The H NMR spectrum shows, in the
same solvent, three singlets at δ = 3.04, 3.12 and 3.43 ppm
(integrating to 6 protons each), which can be assigned to
the three DMSO ligands, and two multiplets at δ = 3.72
and 4.26 ppm (integrating to 2 protons each) corresponding
to the methylene groups of L. Further evidence for the di-
nuclear nature of 1 comes from the FAB-MS spectrum,
which shows signals corresponding to the molecular ion
[M+] and to the fragments [M+ – Cl], [M+ – (DMSO)],
[M+ – 3(DMSO)], [M+ – 3(DMSO) – Cl] and [M+ – Ru –
3(DMSO) – 2Cl]. Two of the three isomers shown in
Scheme 2 are compatible with this structural information.
[a] Departamento de Química Inorgánica, Facultade de Química,
Universidade de Vigo,
36310 Vigo, Spain
Fax: +34-986-813798
E-mail: jbravo@uvigo.es
sgarcia@uvigo.es
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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New Dinuclear Face- and Edge-Sharing Bioctahedral Ru Compounds
FULL PAPER
Scheme 1.
Scheme 2.
Isomer C can be ruled out because the two P nuclei are an AX spin system (δ = 160.7, 151.9 ppm, JAX = 54 Hz)
not equivalent. Isomer A is our preferred choice between and an AB spin system (δ = 148.3 ppm, JAB = 44 Hz),
isomers A and B because the chemical shift of P is similar respectively]. This is a characteristic pattern of compounds
to that observed for compounds with the same environ- of the type [RuCl(PP)(µ-Cl)3Ru(PP)L][10] and can be as-
ment[8] and the methyl groups of each DMSO do not ap- signed to the transoid form of 2 in which the four P atoms
pear as two diastereotopic singlets (we carried out a 2D are not equivalent (see Scheme 3).
1H, 13C HSQC experiment to confirm this, see Supporting
Information) as one would expect them to if they were in
1
proximity to a bidentate ligand. Moreover, the 2D H, 31P
NMR HMBC experiments do not show any evidence of an
interaction between the P atoms and the CH3 protons of
the DMSO ligands (although such negative evidence is not
conclusive).
Figure 1. 31P{1H} NMR spectrum in CDCl3 for compound 2.
Reaction of Compound 1 with L – Preparation of
[Ru2(µ-Cl)3(DMSO)Cl(L)2] (2)
Reaction of 1 with L in a 1:1 molar ratio in refluxing
toluene for 1/2 h gave a yellow solid. The analytical data for
this product are consistent with the formulation [Ru2(µ-Cl)3-
(η2-L)2Cl(DMSO)] (2).[9] The IR spectrum shows a strong
band at 1093 cm–1, which is consistent with the presence of
Scheme 3.
a η1-S sulfoxide ligand.[7]
The 31P{1H} NMR spectrum in CDCl3 shows two sets
The second set of signals consists of two singlets [δ =
of signals. The first set (indicated in Figure 1 by an asterisk) 156.9, 146.4 ppm] (indicated by a double asterisk in Fig-
consists of a pair of doublets and a quartet [consistent with ure 1) and corresponds to the cisoid structure 2b (see
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J. Bravo, S. García-Fontán et al.
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Scheme 4) in which both phosphorus nuclei, belonging to in C6D6 from 25 °C to 45 °C did not provide any evidence
each bidentate ligand, are magnetically equivalent.
for interconversion between them.
Finally, the 13C{1H} spectrum in CD2Cl2 shows two sin-
glets at δ = 50.5 and 51.0 ppm, which can be assigned to
the two inequivalent methyl groups of the DMSO ligand
corresponding to the transoid structure. A signal with a
lower intensity was also observed at δ = 51.3 ppm and this
can be assigned to the two equivalent methyl groups of the
cisoid structure.
We were able to obtain single crystals of the transoid iso-
mer of compound 2 (2a) to carry out an X-ray diffraction
analysis. Selected bond lengths and angles are reported in
Table 1 and an ORTEP view is shown in Figure 2.
Scheme 4.
1
The H NMR spectrum in CDCl3 also presents signals
that correspond to both structures. For example, two sing-
lets at δ = 2.54 and 2.87 ppm can be assigned to the two
diastereotopic methyl groups of DMSO corresponding to
the transoid structure. At 3.22 ppm a singlet with a lower
intensity can be assigned to the methyl groups of the
DMSO ligand corresponding to the cisoid structure (there
Table 1. Bond lengths [Å] and angles [°] for 2a.
Bond lengths
Ru(1)–P(2)
Ru(1)–Cl(4)
2.203(5)
2.377(5)
2.502(5)
2.267(5)
2.260(5)
2.495(4)
Ru(1)–P(1)
Ru(1)–Cl(1)
Ru(1)–Cl(3)
Ru(2)–P(4)
Ru(2)–Cl(3)
Ru(2)–Cl(2)
2.228(5)
2.422(4)
2.551(5)
2.258(5)
2.515(5)
2.395(5)
are no diastereotopic signals in this case because of its Ru(1)–Cl(2)
Ru(2)–P(3)
higher symmetry). A similar situation occurs with the sig-
Ru(2)–S(1)
nals corresponding to the methylene groups of the bidentate
Ru(2)–Cl(1)
ligand. As observed in other halide compounds bearing this
Bond angles
ligand,[11] these groups usually display one multiplet for
P(2)–Ru(1)–P(1)
91.21(19)
P(2)–Ru(1)–Cl(4) 91.86(19)
P(2)–Ru(1)–Cl(1) 96.88(17)
Cl(4)–Ru(1)–Cl(1) 166.02(18)
P(1)–Ru(1)–Cl(2) 92.70(17)
Cl(1)–Ru(1)–Cl(2) 79.28(15)
P(1)–Ru(1)–Cl(3) 170.27(17)
Cl(1)–Ru(1)–Cl(3) 78.32(15)
each proton. In our case different multiplets were observed
that integrate as one proton each and these coexist with
other signals of lower intensity that may correspond to the
P(1)–Ru(1)–Cl(4) 90.28(18)
P(1)–Ru(1)–Cl(1) 100.39(17)
P(2)–Ru(1)–Cl(2) 174.95(18)
Cl(4)–Ru(1)–Cl(2) 91.30(17)
cisoid structure.
An HMBC H,31P{1H} NMR study (see Supporting In- P(2)–Ru(1)–Cl(3) 98.52(18)
1
Cl(4)–Ru(1)–Cl(3) 89.63(17)
formation) shows that there is a correlation between the
signal at δ = 148.3 ppm (in CDCl3) and that at δ = 2.54 ppm
Cl(2)–Ru(1)–Cl(3) 77.57(15)
P(4)–Ru(2)–S(1)
S(1)–Ru(2)–P(3)
93.51(19)
93.99(18)
P(4)–Ru(2)–P(3)
90.14(19)
attributed to one of the DMSO methyl groups. This indi-
cates that – in agreement with the assignment made by Bi-
anchini for a similar complex – this resonance corresponds
to the bidentate ligand coordinated to the Ru atom that
bears the DMSO molecule.[8a] The relative intensities of the
signals of the two isomers change significantly when ben-
P(4)–Ru(2)–Cl(2) 9515(18)
P(3)–Ru(2)–Cl(2) 91.52(17)
S(1)–Ru(2)–Cl(1) 90.95(17)
Cl(2)–Ru(2)–Cl(1) 79.93(15)
S(1)–Ru(2)–Cl(3) 93.26(17)
Cl(2)–Ru(2)–Cl(3) 80.25(16)
Ru(1)–Cl(1)–Ru(2) 86.56(14)
S(1)–Ru(2)–Cl(2) 169.72(17)
P(4)–Ru(2)–Cl(1) 172.99(18)
P(3)–Ru(2)–Cl(1) 94.94(16)
P(4)–Ru(2)–Cl(3) 96.65(18)
P(3)–Ru(2)–Cl(3) 169.73(18)
Cl(1)–Ru(2)–Cl(3) 77.68(15)
Ru(2)–Cl(2)–Ru(1) 86.97(15)
zene is used as the solvent, with the signals of the cisoid Ru(2)–Cl(3)–Ru(1) 83.43(15)
structure almost residual in this case. This must be due to
the different solubility of the two isomers, because a VT
Complex 2 adopts a triply chloride-bridged diruthenium
NMR study carried out in CDCl3 from 25 °C to –50 °C and transoid structure (2a) in which the coordination geometry
Figure 2. ORTEP view of [Ru2(µ-Cl)3(DMSO)Cl(L)2] (2a). The phenyl groups are omitted for clarity.
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New Dinuclear Face- and Edge-Sharing Bioctahedral Ru Compounds
FULL PAPER
at each metal centre is a distorted octahedron. The struc- Reaction of Compound 2 with L – Preparation of
ture is unsymmetrical, with Ru(2) bearing a DMSO and [{RuCl(η2-L)[η1-L(O)]}2(µ-Cl)2] (3)
Ru(1) a chloride ligand. The structural features are similar
to those found in previously reported face-sharing bioctahe-
dral RuII–RuII complexes.[7b,12] The Ru–Clterminal distance is
shorter than the Ru–Clbridge distances. Of all the Ru–Clbridge
distances, those that are trans to a phosphorus atom are the
longest. The shortest Ru–Clbridge distance is that with the
DMSO ligand in the trans position. It is worth noting that
the Ru(1)–P distances (with Ru bound to a terminal chloro
ligand) are significantly shorter than the Ru(2)–P distances
(with Ru bound to the DMSO ligand).
The seven-membered chelate rings allow P–Ru–P angles
of 91.21(19) and 90.14(19)°. The Clbridge–Ru–Clbridge angles
have values between 77.57(15) and 80.25(16)°, with this be-
ing the main source of distortion of the octahedron. As
shown in Figure 3, the environment of the metal atoms cor-
responds with the C1-symmetric transoid isomer, with the
dihedral torsion angle Cl(4)–Ru(1)–Ru(2)–S(1) having a
value of 122.4(2)°. The Ru–Ru distance of 3.371(2) Å lies
in the range expected for this type of dinuclear RuII com-
plex (3.28–3.44 Å).[12a]
The reaction of 2 with L (1:2 molar ratio) in refluxing
toluene for 1 h gave the new compound 3. The 31P{1H}
NMR spectrum in CDCl3 displays a doublet at δ =
159.0 ppm (J = 46 Hz), a triplet at δ = 138.3 ppm and a
singlet at δ = 32.5 ppm with an intensity ratio of 2:1:1,
respectively. The singlet at higher field is consistent with
the existence of a P=O group (corresponding to a partially
oxidised molecule of L) that is not coordinated to the metal.
The other two signals can be assigned to the P atoms of
1
η2-L and η1-L(O), respectively. The H NMR spectrum in
CDCl3 displays four multiplets at 3.68, 3.73, 4.17 and
4.49 ppm with an integral ratio 1:1:1:1. These signals corre-
1
spond to the CH2 groups of the two ligands. The 2D H,
1
1H COSY and the 2D H, 31P HMQC spectra allow full
assignment of those signals (see Exp. Sect.). The FAB mass
spectrum contains peaks at mass values for fragments of
dinuclear species [M+ – Cl – L(O)], [M+ – 2Cl – L(O)],
[M+ – 2Cl – 2L(O)] and, interestingly, the strongest frag-
ment was found at 1013, which corresponds exactly to the
monomeric unit [RuClLL(O)]. Finally, treatment of a sam-
ple of 3 with excess NaBPh4 in ethanol resulted in the pre-
cipitation of a new product, 3Ј. The 31P{1H} NMR spec-
trum of this compound contains two sets of signals: three
pseudotriplets integrating in a 1:1:1 ratio, and a triplet and
a doublet integrating in a 1:2 ratio (the first set integrates
to three times the second one) coexisting with traces of the
original compound (very small signals at 159 and 138 ppm).
When the sample in the NMR tube was stored for five days,
evidence was observed that the reaction had gone back-
wards and the small signals had increased in intensity to
levels similar to those observed at the beginning of the ex-
periment.
All these data suggest the formation of neutral edge-
sharing bioctahedra with two chloro bridges [{RuCl(η2-
L)[η1-L(O)]}2(µ-Cl)2] for compound 3 and this converts
into the cationic face-sharing bioctahedral compound 3Ј by
reaction with NaBPh4 – as depicted in Scheme 5.
Figure 3. Environment of the Ru atoms in 2a.
Scheme 5.
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Reaction of 2 with LЈ [LЈ = PPh3 – n(OEt)n; n = 1–3]
with this situation, the 31P{1H} NMR spectrum of 4Ј in
CDCl3 displays three pseudotriplets at 134.1, 141.9 and
145.7 ppm (corresponding to a transoid isomer) along with
a doublet at δ = 143.3 ppm (the triplet is probably obscured
by the signal at δ = 134.1 ppm) that corresponds to the
cisoid form.
In an effort to complement the results described above
and to gather more information about the reactivity of
complex 2, we investigated the reaction of 2 with the mono-
dentate phosphinite, phosphonite and phosphite ligands of
formulae PPh3–n(OEt)n (n = 1–3) (LЈ). Unexpectedly, dif-
ferent results were obtained when LЈ was changed from a LЈ = PPh(OEt)2 – Preparation of [{Ru(η2-L)-
phosphinite (n = 1) to a phosphite (n = 3).
[PPh(OEt)2]}2(µ-Cl)3]Cl (5)
When a mixture of 2 and PPh(OEt)2 in a 1:2 molar ratio
LЈ = PPh2(OEt) – Preparation of [{RuCl(η2-
L)[PPh2(OEt)]2}2(µ-Cl)2] (4)
was heated under reflux in toluene for 1.5 h, we obtained a
1
solid with 31P{1H} and H NMR spectra consistent with a
When a mixture of 2 and PPh2(OEt) in a 1:2 molar ratio mixture (approx. 1:3) of both cisoid and transoid isomers of
was heated under reflux in toluene for 1 h, the new com- the cationic trichloro-bridged dinuclear compound [{Ru(η2-
pound [{RuCl(η2-L)[PPh2(OEt)]2}2(µ-Cl)2] (4) was ob- L)[PPh(OEt)2]}2(µ-Cl)3]Cl (5) (see Scheme 1). The 31P{1H}
tained. Compound 4 shows spectral features that are very NMR spectrum displays a doublet at δ = 151.7 ppm and a
similar to those of compound 3. The 31P{1H} NMR spec- triplet at δ = 158.2 ppm (J = 53 Hz) (cisoid isomer) and
trum shows a doublet at δ = 159.7 ppm and a triplet at δ = three pseudotriplets at 149.7, 153.0 and 156.1 ppm (transoid
1
136.3 ppm (integrating to 2:1, J = 46 Hz), which are very isomer). Careful inspection of the H NMR spectrum also
similar to the signals of 3. The 1H NMR spectrum also enables the signals of both isomers to be assigned (see Exp.
contains a set of signals that is consistent with this formula- Sect.). The mass spectrum shows the [M+] peak at m/z =
tion. The signals at 4.31 (m, 4 H) and 3.86 (m, 4 H) ppm 1567, which is consistent with a dinuclear formulation.
can be assigned to the –CH2– groups of the bidentate ligand Moreover, treatment of a solution of this complex with ex-
L, and those at 3.50 (m, 4 H) and 1.22 (t, 6 H) can be cess NaBPh4 in ethanol gave a tan solid with spectral fea-
assigned to the ethoxy group of LЈ. The FAB mass spec- tures identical to those of the original product, thus con-
trum of 4 displays (as observed for compound 3) peaks that firming its ionic nature. We were also able to obtain suitable
indicate the dinuclear nature of the compound: 1630 crystals for an X-ray diffraction study. The structure of the
(M+ – Cl), 1435 (M+ – LЈ), 1400 (M+ – LЈ – Cl), 830 complex cation and the most relevant distances and angles
[RuCl2LLЈ]+, 797 [RuClLLЈ]+.
are shown in Figure 4 and in Tables 2 and 3, respectively.
Treatment of a sample of 4 with excess NaBPh4 in etha-
It can be seen that the cation complex 5a adopts a
nol gave similar results to those obtained in the case of transoid [dihedral torsion angle P(1)–Ru(1)–Ru(2)–P(2) of
complex 3, with a new dinuclear face-shared bioctahedral 115.5(2)°] triply chloride-bridged diruthenium structure
complex, 4Ј, formed as a mixture of both cisoid and transoid similar to 2a (Figure 5). The coordination geometry around
isomers.[13] However, in this case the proportion of the each metal centre is a distorted octahedron, with the same
transoid isomer for the face-shared bioctahedra is signifi- coordination sphere at each ruthenium atom (three bridging
cantly greater than in the case of compound 3. In agreement chlorine atoms and three phosphorus atoms). The two met-
Figure 4. The cation of [{Ru(η2-L)[PPh(OEt)2]}2(µ-Cl)3]Cl (5a) drawn at 20% probability level. The phenyl rings were replaced by spheres
of arbitrary radius.
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New Dinuclear Face- and Edge-Sharing Bioctahedral Ru Compounds
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Table 2. Selected bond lengths [Å] and angles [°] for complex cation
5a.
Bond lengths
Ru(1)–Cl(3)
Ru(1)–Cl(2)
Ru(1)–P(12)
Ru(2)–Cl(3)
Ru(2)–Cl(4)
Ru(2)–P(21)
Ru(2)–Ru(1)
2.478(3)
2.535(3)
2.261(3)
2.495(3)
2.473(2)
2.284(3)
3.4417(12)
Ru(1)–Cl(4)
Ru(1)–P(1)
Ru(1)–P(11)
Ru(2)–Cl(2)
Ru(2)–P(2)
Ru(2)–P(22)
2.482(2)
2.241(3)
2.274(3)
2.511(3)
2.253(3)
2.265(3)
Bond angles
P(1)–Ru(1)–P(12)
P(12)–Ru(1)–P(11) 89.89(11)
P(12)–Ru(1)–Cl(3) 94.82(11)
89.78(12)
P(1)–Ru(1)–P(11)
P(1)–Ru(1)–Cl(3)
P(11)–Ru(1)–Cl(3)
P(12)–Ru(1)–Cl(4)
P(1)–Ru(1)–Cl(2)
P(11)–Ru(1)–Cl(2)
Cl(4)–Ru(1)–Cl(2)
P(2)–Ru(2)–P(22)
P(22)–Ru(2)–P(21)
P(22)–Ru(2)–Cl(4)
P(2)–Ru(2)–Cl(3)
P(21)–Ru(2)–Cl(3)
P(22)–Ru(2)–Cl(2)
Cl(4)–Ru(2)–Cl(2)
Cl(4)–Ru(2)–Cl(3)
Ru(1)–Cl(3)–Ru(2)
93.54(11)
95.13(11)
170.14(10)
99.34(10)
93.28(11)
98.19(11)
76.95(8)
94.45(11)
90.05(10)
170.80(10)
168.04(11)
99.34(10)
98.72(10)
77.56(8)
P(1)–Ru(1)–Cl(4)
169.52(10)
P(11)–Ru(1)–Cl(4) 91.65(10)
P(12)–Ru(1)–Cl(2) 171.16(11)
Cl(3)–Ru(1)–Cl(2) 76.66(9)
Cl(3)–Ru(1)–Cl(4) 79.05(8)
P(2)–Ru(2)–P(21)
P(2)–Ru(2)–Cl(4)
P(21)–Ru(2)–Cl(4) 93.22(9)
P(22)–Ru(2)–Cl(3) 92.09(10)
P(2)–Ru(2)–Cl(2)
P(21)–Ru(2)–Cl(2) 170.49(9)
Cl(3)–Ru(2)–Cl(2) 76.80(9)
Ru(2)–Cl(2)–Ru(1) 86.02(8)
Ru(2)–Cl(4)–Ru(1) 87.99(8)
Figure 5. Environment of the Ru atoms in the complex cation 5a.
pected for this type of dinuclear RuII complex, 3.28–
3.44 Å.[12a]
90.66(11)
94.10(10)
LЈ = P(OEt)3 – Preparation of [RuCl2(η2-L){P(OEt)3}2]
(6)
92.30(11)
When a mixture of 2 and P(OEt)3 in a 1:2 molar ratio
was heated under reflux in toluene for 1 h, we obtained a
solid that has NMR features consistent with a mononuclear
species of formula [RuCl2(η2-L){P(OEt)3}2] (6), in which
one bidentate ligand and two phosphite ligands (mutually
78.90(8)
87.59(9)
Table 3. Hydrogen bonding parameters for complex cation 5a [Å cis) are present. The 31P{1H} NMR spectrum consists of
and °].
four double doublets of doublets at 97.8 (P1), 122.0 (P4),
129.8 (P2) and 150.7 (P3) ppm (J12 = 48, J13 = 24, J14
=
D–H···A
d(D–H) d(H···A) d(D···A)
blab-
la(DHA)
1
544, J23 = 47, J24 = 64 and J34 = 46 Hz). The H NMR
spectrum displays two triplets at δ = 0.90 and 1.22 ppm (J
= 7 Hz), which integrate to 9 protons each, and these sig-
nals can be assigned to the methyl groups of LЈ. These sig-
nals demonstrate the nonequivalence of the two ligands.
The signals corresponding to the methylene protons of both
C(3)–H(3B)···Cl(1A) 0.97
C(1)–H(1A)···Cl(1)
C(2)–H(2A)···Cl(1)
2.79
2.93
2.89
3.500(9)
3.586(10) 125.7
3.610(10) 131.3
131.1
0.97
0.97
als maintain the same oxidation state (+II) as a disordered L and LЈ appear as seven multiplets of different intensity.
1
chloride ion is acting as a counterion. Two of the phospho- These signals were fully characterised by 2D H, 13C{1H}
rus atoms coordinated to each metal atom come from the HSQC correlation (see Figure 6). The methylene protons of
bidentate phosphinite ligand L, and the third one comes the bidentate ligand L appear as four multiplets at 3.43,
from the monodentate ligand LЈ. In contrast to complex 3.98, 4.40 and 5.67 ppm, integrating to one proton each.
2a, the environment around each ruthenium atom is quite On the other hand, the methylene protons of both LЈ li-
similar, with similar values for bond lengths and angles. The gands appear as four multiplets centred at 3.26, 3.43, 4.23
Ru–P bonds are slightly shorter, by 0.01 Å, when the ligand and 4.46 and these signals integrate to three protons each
is the monodentate phosphonite ligand. The Ru–Cl bond because of the nonequivalence of the two LЈ ligands and the
lengths range from 2.473(2) to 2.535(3) Å, with the longer diastereotopic nature of each pair of geminal CH2 protons.
ones corresponding to those including the labelled Cl(2)
Crystals suitable for X-ray analysis were obtained. The
atom, the only one that is simultaneously trans to two phos- structure of the complex is shown in Figure 7 and the most
phinite phosphorus atoms. The Ru(1)–Cl(2)–Ru(2) angle, relevant distances and angles are given in Table 4. The com-
86.02(8)°, is also the most acute of the three Ru–Cl–Ru pound consists of discrete units in which the ruthenium
angles.
atom is in a slightly distorted octahedral environment, coor-
The seven-membered chelate rings allows P–Ru–P angles dinated to two mutually cis chlorine atoms, two phosphorus
of 89.89(11) and 90.05(10)°, which are virtually identical to atoms of a diphosphinite ligand and two phosphorus atoms
one another and similar to those found in 2a. The Cl–Ru– of two monodentate phosphite ligands, which are also mu-
Cl angles involving the triple bridge have values between tually cis. The cis angles range from 84.78(5) to 97.28(6)°,
76.66(9) and 79.05(8)° and once again this is the main with the latter value corresponding to the chelate angle al-
source of distortion of the octahedron. The Ru–Ru separa- lowed by the seven-membered chelate ring. The trans angles
tion of 3.4417(12) Å is in the upper limit of the range ex- range from 170.42(6) to 177.02(6)° and these show the regu-
Eur. J. Inorg. Chem. 2006, 3028–3040
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3033

J. Bravo, S. García-Fontán et al.
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Table 4. Selected bond lengths [Å] and angles [°] for complex 6.
Bond lengths
Ru–P(4)
Ru–P(3)
Ru–Cl(2)
2.2333(17)
2.3040(17)
2.4633(15)
Ru–P(1)
Ru–P(2)
Ru–Cl(1)
2.2777(15)
2.4406(16)
2.4675(15)
Bond angles
P(4)–Ru–P(1)
P(1)–Ru–P(3)
P(1)–Ru–P(2)
P(4)–Ru–Cl(2)
P(3)–Ru–Cl(2)
P(4)–Ru–Cl(1)
P(3)–Ru–Cl(1)
Cl(2)–Ru–Cl(1)
93.48(6)
92.24(6)
97.28(6)
177.02(6)
91.85(6)
93.95(5)
84.78(5)
86.81(5)
P(4)–Ru–P(3)
P(4)–Ru–P(2)
P(3)–Ru–P(2)
P(1)–Ru–Cl(2)
P(2)–Ru–Cl(2)
P(1)–Ru–Cl(1)
P(2)–Ru–Cl(1)
91.09(6)
89.36(6)
170.42(6)
85.91(5)
87.82(5)
172.04(6)
85.65(5)
Reaction of [RuCl2(DMSO)4] with L in a 1:2 Molar Ratio
Figure 6. 2D 1H,13C{1H} HSQC experiment in CDCl3 for com-
pound 6. Signals in the 13C spectrum can be assigned as follows: δ
= 65.9, 62.6 (br. s, CH2, L), 62.9, 61.9 (d, JCP = 10 Hz, CH2, LЈ).
Signals marked with an asterisk correspond to an impurity.
A mixture of [RuCl2(DMSO)4] and L in a 1:2 molar ratio
was heated under reflux in toluene for 2 h and the pro-
gression of the reaction was followed by 31P NMR spec-
troscopy. A complicated spectrum was observed with dif-
ferent sets of signals, suggesting the presence of a mixture
larity of the octahedron, which is probably only distorted of several new compounds. The solution was evaporated to
due the steric hindrance of the diphosphinite ligand. The dryness and the residue was treated with Et2O. An orange
cis Cl–Ru–Cl angle, 86.81(5)°, is similar to those found in solid and a yellow solution were obtained. The solid was
cis complexes RuCl2P4.[14] The Ru–Cl distances are similar filtered off, washed with Et2O and dried to afford the same
to one another but the Ru–P distances show small differ- compound, [{RuCl(η2-L)[η1-Ph2PO(CH2)2OP(O)Ph2]}2(µ-
ences in the order Ru–P4 Ͻ Ru–P1 Ͻ Ru–P3 Ͻ Ru–P2. Cl)2] (3), as was already obtained in the reaction of complex
This order is consistent with the greater trans influence of 2 with L.[15] The yellow solution was purified by column
phosphorus ligands than Cl and the higher π-acceptor char- chromatography to yield the two new compounds
acter of phosphite ligands as compared with phosphinites.
[RuCl2(L)(Ph2POPPh2)] (7) and [RuCl(CO)(L)(Ph2PO-
Figure 7. ORTEP representation of complex [RuCl2(η2-L){P(OEt)3}2] (6) drawn at the 30% probability level. The phenyl rings were
replaced by spheres of arbitrary radius.
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New Dinuclear Face- and Edge-Sharing Bioctahedral Ru Compounds
FULL PAPER
CH2)] (8) (see Exp. Sect. for details). We were able to obtain periment by the cross-peak present with the methylene sig-
single crystals of both compounds that were suitable for X- nal of L at δ = 4.30 ppm, see Supporting Information) and
ray analysis.
the multiplet at δ = 106.8 ppm can be assigned to the phos-
phorus nuclei of the tetraphenyldiphosphoxane ligand. The
IR spectrum contains a strong band at 791 cm–1 and this
is assigned to the P–O–P asymmetric stretching mode in
accordance with its chelating nature (reported values of
775–800 cm–1).[16,20]
An ORTEP view of compound 7 is shown in Figure 8
along with the labelling scheme. Selected distances and
angles are given in Table 5. The compound consists of dis-
crete units, although some intermolecular nonclassical
Cl···HC hydrogen bonds can be found (Table 6). The ruthe-
nium atom is in a distorted octahedral environment and is
coordinated to two chlorine atoms that are mutually trans,
two phosphorus atoms of a tetraphenyldiphosphoxane li-
gand and two phosphorus atoms of a diphosphinite ligand.
[RuCl2(L)(Ph2POPPh2)] (7)
The reaction probably involves a metal-promoted disrup-
tion of the bidentate ligand to tetraphenyldiphosphox-
ane,[16] although in a somewhat similar reaction between
[Rh(COE)2Cl]2 (COE = cyclooctene) and P(NMe2)3 in tolu-
ene, the generation of a diphosphoxane complex was attrib-
uted to a hydrolysis impurity present in the commercial
P(NMe2)3.[17] This is probably not the situation in our case
because we did not observe such a process in reactions be-
tween the same ligand and other metals such as Re and
Mn.[18] Other authors have observed the same product
(POP) and suggested a P–P(O) to P–O–P thermal re-
arrangement prior to metal coordination,[19] a process that
is favoured when R groups bonded to P are inductively elec-
tron-withdrawing groups like OR groups (as in our case).
A likely mechanism involves partial hydrolysis of the ligand
due to the prolonged heating and the presence of adven-
titious moisture, followed by a tautomeric rearrangement
from the P–P(O) to the P–O–P form.
Table 5. Bond lengths [Å] and angles [°] for compound 7.
Bond lengths
Ru(1)–P(2)
Ru(1)–P(3)
Ru(1)–Cl(1)
O(1)–P(4)
2.3271(7)
2.3783(7)
2.4237(7)
1.6593(17)
Ru(1)–P(1)
Ru(1)–P(4)
Ru(1)–Cl(2)
O(1)–P(3)
2.3423(7)
2.4119(7)
2.4280(7)
1.6652(17)
The 1H NMR spectrum of 7 in CDCl3 shows a multiplet
centred at δ = 4.30 ppm, which is assigned to the methylene
protons of the bidentate diphosphinite ligand, and signals
between 6.90 and 7.50 ppm corresponding to the phenyl
groups of the two chelating ligands. The 31P{1H} NMR
spectrum in CDCl3 shows two doublets of multiplets
centred at δ = 106.8 and 133.0 ppm, corresponding to the
two phosphorus nuclei of each bidentate ligand. The signal
at lower field can be assigned to the bisphosphinite ligand
Bond angles
P(1)–Ru(1)–P(2)
P(2)–Ru(1)–P(3)
P(1)–Ru(1)–P(3)
P(2)–Ru(1)–Cl(1) 98.32(3)
P(3)–Ru(1)–Cl(1) 84.41(2)
P(2)–Ru(1)–Cl(2) 90.25(3)
P(3)–Ru(1)–Cl(2) 93.75(3)
Cl(1)–Ru(1)–Cl(2) 171.40(2)
92.43(3)
98.56(2)
168.91(2)
P(3)–Ru(1)–P(4)
P(1)–Ru(1)–P(4)
P(2)–Ru(1)–P(4)
P(1)–Ru(1)–Cl(1) 92.53(3)
P(4)–Ru(1)–Cl(1) 84.58(2)
P(1)–Ru(1)–Cl(2) 87.69(3)
P(4)–Ru(1)–Cl(2) 86.99(2)
66.37(2)
102.76(3)
164.42(3)
P(4)–O(1)–P(3)
104.14(9)
L (as shown in the 2D H, 31P{1H} HMBC correlation ex-
1
Figure 8. ORTEP drawing of the complex [RuCl2(L)(Ph2POPPh2)] (7).
Eur. J. Inorg. Chem. 2006, 3028–3040
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3035

J. Bravo, S. García-Fontán et al.
FULL PAPER
The four phosphorus atoms are located in the equatorial phosphorus atoms (rms = 0.057). The plane defined by the
plane (rms = 0.057). The chelate ring angle of the tet- two phosphorus atoms and the two oxygen atoms of the
raphenyldiphosphoxane ligand is only 66.37(2)° and is the diphosphinite ligand (rms = 0.088) forms a dihedral angle
main source of distortion. To the best of our knowledge, with the equatorial plane of 41.73(6)°. However, the plane
this is the first example of a ruthenium complex with this P(3)–Ru–P(4) forms a dihedral angle of only 6.00(7)° with
type of chelating ligand, but the chelate angle is similar to the equatorial plane and can essentially be considered as
that found in the chromium, molybdenum and rhodium coplanar [the oxygen atom O(1) is only 0.096(2) Å out of
complexes.[17,21] The chelate angle allowed by the seven- the equatorial plane].
membered chelate ring is close to the theoretical value of
90° [92.43(3)°] and, consequently, the other two angles in
the equatorial plane increase to 98.56(2) and 102.76(3)°.
The trans Cl–Ru–Cl angle is also slightly different than the
[RuCl(CO)(L)(Ph2POCH2)] (8)
Compound 8 has a surprising structure in which the ru-
thenium centre is coordinated by an intact ligand L, Cl and
CO ligands, and an anionic fragment Ph2POCH2 of this
–
expected value of 180° [171.40(2)°] and this is due to a small
ligand. This arrangement stabilises, in spite of the strain, a
deviation of the chlorine atom labelled as Cl(1), as shown
ruthena-phospha-oxa-cyclobutane ring. As the only source
by the P–Ru–Cl angles. The four-membered chelate ring is
almost planar, with the O(1) atom only 0.103(2) Å out of
the P(3)–Ru–P(4) plane.
of CO is the bis(phosphinite) L ligand, and we did not ob-
serve similar behaviour for L with other metals,[18] these
fragments must come from a metal-promoted disruption of
the bidentate ligand. Moreover, although the yields are low,
Table 6. Hydrogen bond parameters for 7 [Å and °].[a]
the reaction is perfectly reproducible. The complex was
D–H···A
d(D–H) d(H···A) d(D···A) blab-
la(DHA)
characterised in solution by multinuclear NMR spec-
troscopy. The 31P{1H} NMR spectrum of 8 in CDCl3
shows three doublet of doublets, which is consistent with a
structure presenting two mutually trans phosphorus atoms
C(2)–H(2B)···Cl(2)
C(12)–H(12)···Cl(1)
C(32)–H(32)···Cl(2)
C(56)–H(56)···Cl(1)
C(86)–H(86)···Cl(2)
0.97
0.93
0.93
0.93
0.93
2.61
2.61
2.69
2.69
2.82
2.87
3.397(3) 138.8
3.234(3) 124.8
3.506(3) 147.2
3.302(3) 124.3
3.423(3) 123.8
3.738(3) 156.5
–
[one on the Ph2POCH2 fragment (δ = 76.0 ppm) and one
on the L ligand (δ = 133.3 ppm), Jtrans = 341 Hz] and the
other in a cis disposition (δ = 131.5 ppm), Jcis = 14 and
C(85)–H(85)···Cl(2)#1 0.93
[a] Symmetry transformations used to generate equivalent atoms:
1 – x, y + 1/2, 1/2 – z.
1
31 Hz. The H NMR spectrum of 8 in CDCl3 shows two
groups of multiplets, one in the range 3.80–4.80 ppm that
The angle P(4)–O(1)–P(3) has a value of 104.14(9)°, integrates to six protons and corresponds to the methylene
which is slightly less acute than those reported for the afore- groups of the two ligands, and other between 7.20–7.80 (30
mentioned complexes.[17,21] The ruthenium atom is only H) that corresponds to the phenyl groups. An HMBC
0.0184(4) Å out of the equatorial plane defined by the four 31P{1H}–1H correlation enabled identification of the dif-
Figure 9. ORTEP drawing of complex 8.
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Eur. J. Inorg. Chem. 2006, 3028–3040

New Dinuclear Face- and Edge-Sharing Bioctahedral Ru Compounds
FULL PAPER
ferent proton signals, showing that the multiplets at δ = 3.97 Table 8. Hydrogen-bonding parameters for complex 8 [Å and °].[a]
and 4.77 ppm (integrating to 2 protons each) can be as-
D–H···A
d(D–H)
d(H···A) d(D···A) blab-
la(DHA)
signed to the methylene groups of L, and the multiplets at
δ = 4.52 and 4.68 ppm (integrating to one proton each)
correspond to the CH2 group bonded to the ruthenium.
C(43)–H(43)···Cl(1Ј) 0.93
C(36)–H(36)···O(4) 0.93
2.95
2.48
2.46
3.743(10) 143.8
2.854(11) 104.1
2.871(11) 107.2
This observation shows that these two protons are dia- C(56)–H(56)···O(3) 0.93
stereotopic.
[a] Symmetry transformations used to generate equivalent atoms: Ј
x – 1, y, z.
An ORTEP view of compound 8 is shown in Figure 9
along with the labelling scheme. Selected distances and
angles are given in Table 7. The compound consists of dis-
crete units, although some intermolecular nonclassical
Cl···HC hydrogen bonds can be found (see Table 8). The
ruthenium atom is in a distorted octahedral environment,
coordinated to one chlorine atom, two phosphorus atoms
of a diphosphinite ligand, one phosphorus atom, a carbon
atom of the diphenyl(oxymethyl-κC)phosphinite-κP ligand
and a carbon atom of a carbonyl ligand. Two of the ligands
act as bidentate systems (diphosphinite and phosphinite li-
gand) and these can be considered to be in the equatorial
plane. The four-membered chelate ring is one of the main
sources of distortion in the octahedron, with an angle of
62.9(3)°. The opposite seven-membered chelate angle in the
equatorial plane is slightly larger than one would expect for
this ligand, 93.59(9)°, but the two adjacent angles in the
equatorial plane do not increase to the same extent [P(1)–
Ru(1)–P(3) = 110.85(9)°, C(1)–Ru(1)–P(2) = 92.4(3)°]. The
differences found in these angles are due to the steric effects
of the phenyl rings on the phosphorus atoms. For the same
reason, all the axial angles in the octahedron are close to
the expected 180°, except for the P(2)–Ru(1)–P(1) angle
[155.26(9)°]. The plane formed by the four atoms in the che-
late ring (rms = 0.069) forms a dihedral angle of only
7.2(2)° with the equatorial plane of the donor atoms (rms
= 0.047). The ruthenium atom is only 0.096(3) Å out of this
plane.
Conclusions
New dinuclear ruthenium complexes bearing the 1,2-
bis(diphenylphosphinite)ethane ligand in different pro-
portions were prepared and characterised. The compounds
[Ru2(µ-Cl)3(DMSO)3Cl(η2-L)] (1) and [Ru2(µ-Cl)3(DMSO)-
Cl(η2-L)2] (2) present a face-sharing bioctahedral structure
while compound [Ru2Cl2(η2-L)2{η1-L(O)}2(µ-Cl)2] (3) has
an edge-sharing bioctahedral structure with two chelating
L units and two monodentate ligands in which a phospho-
rus atom is oxidised and remains uncoordinated. Reaction
of compound 2 [a mixture of both cisoid (2a, minor compo-
nent) and transoid (2b, major component) isomers] with the
monodentate ligands PPh3–n(OEt)n (n = 1–3) (LЈ) affords
different compounds depending on the structure of LЈ.
When LЈ is structurally similar to L (both phosphinites),
the resulting compound is the dinuclear doubly chloro-
bridged complex [{RuCl(η2-L)(LЈ)}(µ-Cl)2] (4), which is
very similar to compound 3 – obtained by reacting com-
pound 2 with L. Reaction of compound 2 with the phos-
phonite LЈ (n = 2) gave the face-sharing octahedral com-
pound [{Ru(η2-L)(LЈ)}2(µ-Cl)3]Cl (5) as a mixture of both
cisoid (5a) and transoid (5b) isomers. On the other hand,
when LЈ is a phosphite (n = 3) the reaction with compound
2 yields the mononuclear compound [RuCl2(η2-L)(LЈ)2] (6).
Finally, compound 3 can also be obtained by reaction of
[RuCl2(DMSO)4] with L, but in this case two more prod-
ucts with formulae [RuCl2(L)(Ph2POPPh2)] (7) and
[RuCl(CO)(L)(Ph2POCH2)] (8) were also obtained. In these
products a chelating diphosphinite L coexists with new
phosphorus ligands formed in situ by metal-mediated dis-
ruptions of L.
Table 7. Selected bond lengths [Å] and angles [°] for complex 8.
Bond lengths
Ru(1)–C(2)
Ru(1)–P(2)
Ru(1)–P(3)
P(1)–O(1)
1.835(11)
2.336(3)
2.378(3)
1.582(6)
Ru(1)–C(1)
Ru(1)–P(1)
Ru(1)–Cl(1)
O(1)–C(1)
2.181(10)
2.346(3)
2.467(2)
1.465(11)
Experimental Section
Bond angles
C(2)–Ru(1)–C(1)
C(1)–Ru(1)–P(2)
C(1)–Ru(1)–P(1)
C(2)–Ru(1)–P(3)
P(2)–Ru(1)–P(3)
C(2)–Ru(1)–Cl(1) 174.0(3)
P(2)–Ru(1)–Cl(1) 87.09(8)
P(3)–Ru(1)–Cl(1) 88.64(8)
89.8(4)
92.4(3)
62.9(3)
97.3(3)
93.59(9)
C(2)–Ru(1)–P(2) 91.9(3)
C(2)–Ru(1)–P(1) 88.8(3)
P(2)–Ru(1)–P(1) 155.26(9)
C(1)–Ru(1)–P(3) 170.5(3)
P(1)–Ru(1)–P(3) 110.85(9)
C(1)–Ru(1)–Cl(1) 84.3(3)
P(1)–Ru(1)–Cl(1) 89.60(8)
O(2)–C(2)–Ru(1) 176.2(9)
General: All experimental manipulations were carried out under
argon using Schlenk techniques. All solvents were purified by con-
ventional procedures[23] and distilled prior to use. [RuCl2-
(DMSO)4][24] and 1,2-bis(diphenylphosphanyloxy)ethane[18c] were
prepared using published methods. All the other chemicals were
commercial products and were used as received without further
purification. 1D and 2D NMR spectra (δ, ppm) were recorded in
CDCl3, CD2Cl2 or C6D6 (as indicated) with a Bruker ARX-400
spectrometer (161 MHz for 31P{1H}, 100 MHz for 13C{1H},
400 MHz for 1H) using the solvent as the internal lock. 31P{1H}
chemical shifts are referred to 85% H3PO4 with downfield values
To the best of our knowledge, the diphenyl(oxymethyl-
κC)phosphinite-κP ligand has only previously been found
to show this behaviour in the manganese complex tetra-
carbonyl-2,2-diphenyl-1-oxa-2-phospha-3-manganacyclo-
butane.[22]
1
reported as positive. H and 13C{1H} signals are referred to resid-
ual protonated solvents as internal standards. IR spectra of samples
in KBr pellets were obtained with a Bruker Vector IFS28 FT spec-
trophotometer. Mass spectra were recorded with a Micromass Au-
Eur. J. Inorg. Chem. 2006, 3028–3040
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J. Bravo, S. García-Fontán et al.
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tospec M LSIMS (FAB+) system with 3-nitrobenzyl alcohol as ma-
trix. Microanalyses were carried out with a Fisons EA-1108 appa-
ratus. Merck silica gel 60 (0.040–0.063 mm) was used for column
chromatography.
0.72 g (42%). C104H96Cl4O10P8Ru2 (2097.61): calcd. C 59.55, H
4.61; found C 59.20, H 4.63. H NMR (CDCl3): δ = 3.68 (m, 4 H,
1
CH2, L), 3.73 [m, 4 H, CH2, L(O)], 4.17 [m, 4 H, CH2, L(O)], 4.49
(m, 4 H, CH2, L), 6.80–8.00 (m, 80 H, Ph) ppm. 31P{1H} NMR
(CDCl3): δ = 32.5 [s, (P=O), L(O)], 138.3 [t, J = 46 Hz, P, L(O)],
159.0 (d, J = 46 Hz, 2P, L) ppm. FAB+/MS: m/z (calculated for the
most abundant isotopes) 1617 [M+ – Cl – L(O)], 1580 [M+ – 2Cl –
L(O)], 1013 [RuClLL(O)]+.
Synthesis of [Ru2(µ-Cl)3(DMSO)3Cl(L)] (1): A solution of L
(2.0 mL, 0.56 mmol) in toluene was added to a solution of
[RuCl2(DMSO)4] (0.5 g, 1.03 mmol) in toluene (20 mL). The solu-
tion was heated under reflux for 1/2 h, cooled to room temperature
and concentrated under vacuum. The residue was treated with
EtOH to give a yellow solid, which was washed with EtOH and
dried under vacuum. Yield: 0.40 g (77%). C32H42Cl4O5P2Ru2S3
(108.77): calcd. C 38.10, H 4.20, S 9.54; found C 37.97, H 4.19, S
9.50. 1H NMR (CDCl3): δ = 3.04 (s, 6 H, DMSO), 3.12 (s, 6 H,
DMSO), 3.43 (s, 6 H, DMSO), 3.72 (m, 2 H, CH2), 4.26 (m, 2 H,
CH2), 7.29 (m, 12 H, Ph), 7.49 (m, 4 H, Ph), 7.78 (m, 4 H, Ph).
31P{1H} NMR (CDCl3): δ = 158.2 (s). IR (KBr): ν(SO) 1093 (s)
cm–1. FAB+/MS: m/z (calculated for the most abundant isotopes)
Synthesis of [Ru2(µ-Cl)2Cl2(L)2{PPh2(OEt)}2] (4): PPh2(OEt)
(0.05 mL, 0.24 mmol) was added to a solution of compound 2
(0.150 g, 0.12 mmol) in toluene (20 mL). The mixture was heated
under reflux for 1 h and the solvent was removed under vacuum.
Addition of Et2O gave an orange-yellow precipitate and this was
filtered off, washed with Et2O and dried under vacuum. Yield:
0.15 g (75%). C80H78Cl4O6P6Ru2 (1665.27): calcd. C 57.70, H 4.72;
1
found C 57.53, H 4.71. H NMR (CDCl3): δ = 1.22 (t, J = 7 Hz,
6 H, CH3), 3.50 (m, 4 H, OCH2), 3.86 (m, 4 H, CH2), 4.31 (m, 4
H, CH2), 6.50–7.90 (m, 60 H, Ph) ppm. 31P{1H} NMR (CDCl3): δ
= 136.3 (t, J = 46 Hz, P, LЈ), 159.7 (d, J = 46 Hz, 2P, L) ppm.
FAB+/MS: m/z (calculated for the most abundant isotopes) 1631
(M+ – Cl), 1436 (M+ – LЈ), 1401 (M+ – LЈ – Cl), 832 [RuCl2-
LLЈ]+, 797 [RuClLLЈ]+.
= 1010, (M+), 975 (M+ – Cl), 932 (M+ – DMSO), 776 (M+
3DMSO), 741 (M+ – 3DMSO – Cl), 602 [RuCl2L]+.
–
Synthesis of [Ru2(µ-Cl)3(DMSO)Cl(L)2] (2): Method (a): A solution
of L (1.8 mL, 0.50 mmol) in toluene was added to a solution of 1
(0.50 g, 0.49 mmol) in toluene (20 mL). The solution was heated
under reflux for 1/2 h and then cooled to room temperature. The
solvent was removed under vacuum and EtOH was added to the
oily residue. The resulting yellow precipitate was filtered off,
washed with EtOH and dried under vacuum. Yield: 0.43 g (68%).
Method (b): A solution of L (4.0 mL, 1.14 mmol) in toluene was
added to a solution of [RuCl2(DMSO)4] (0.5 g, 1.03 mmol) in tolu-
ene (20 mL). The reaction mixture was heated under reflux for 1 h
and then cooled to room temperature. The solvent was removed
under vacuum and EtOH was added to the oily residue. The re-
sulting yellow precipitate was filtered off, washed with EtOH and
dried under vacuum. Yield: 0.39 g (59%). C54H54Cl4O5P4Ru2S
(1282.92): calcd. C 50.55, H 4.24, S 2.50; found C 50.32, H 4.26, S
2.55. 1H NMR (CDCl3) (intensity ratio 1:4 cisoid/transoid isomers):
δ = 2.54 (s, 3 H, CH3ЈSO, transoid), 2.87 (s, 3 H, CH3ЈЈSO,
transoid), 3.22 (s, 6 H, DMSO, cisoid), 3.57–4.13 [m, (5 H, CH2,
transoid + 5 H, CH2, cisoid)], 4.33 [m, (1 H, CH2, transoid + 1 H,
CH2, cisoid)], 4.50 (m, 1 H, CH2, cisoid), 4.59 (m, 1 H, CH2, cisoid),
4.76 (m, 1 H, CH2, transoid), 4.90 (m, 1 H, CH2, transoid), 6.80–
8.30 [m, (40 H, Ph, cisoid + 40 H, Ph, transoid)] ppm. 31P{1H}
NMR (CDCl3): δ = 146.4 (s, cisoid), 148.3 (q, JAB = 44 Hz,
transoid), 151.9 (d, JAX = 55 Hz), 156.9 (s, cisoid), 160.7 (d, J =
55 Hz, transoid) ppm. C54H54Cl4O5P4Ru2S: calcd. C 50.55, H 4.24,
S 2.50; found C 49.82, H 4.28, S 2.67. FAB+/MS: m/z (calculated
for the most abundant isotopes) 1284 (M+), 1249 (M+ – Cl), 1206
(M+ – DMSO). X-ray quality crystals were obtained by slow evapo-
ration of a CH2Cl2/Et2O (1:10 v/v) solution.
Synthesis of [Ru2(µ-Cl)3(L)2{PPh(OEt)2}2]Cl (5): PPh(OEt)2
(0.07 mL, 0.24 mmol) was added to a solution of compound 2
(0.150 g, 0.12 mmol) in toluene (20 mL). The mixture was heated
under reflux for 1.5 h and the solvent was removed under vacuum.
Addition of Et2O gave a yellow precipitate and this was filtered off,
washed with Et2O and dried under vacuum. Yield: 0.13 g (67%).
C72H78Cl4O8P6Ru2 (1601.18): calcd. C 54.01, H 4.91; found C
1
53.81, H 4.88. H NMR (CDCl3): δ = 0.83 (t, 6 H, J = 7 Hz, CH3,
transoid), 0.97 (t, 6 H, J = 7 Hz, CH3, transoid), 1.25 (m, 12 H,
CH3, cisoid), 3.50–3.90 [m, 16 H, CH2 (L + LЈ), transoid], 4.01 [m,
8 H, CH2 (LЈ), cisoid], 4.26 [m, 4 H, CH2, (L)], 4.51 [m, 4 H, CH2,
(L)], 6.40–8.00 [m, (50 H, Ph, cisoid) + (50 H, Ph, transoid)] ppm.
31P{1H} NMR (CDCl3): δ = 149.6 [tapparent, Japp = 48 Hz, 2P (L),
transoid], 151.7 [d, J = 53 Hz, 4P (L), cisoid], 153.0 [tapparent, Japp
= 48 Hz, 2P (L), transoid], 156.1 [tapparent, Japp = 53 Hz, 2P (LЈ),
transoid], 158.2 [t, J = 53 Hz, 2P (LЈ), cisoid] ppm. FAB+/MS m/z
(calculated for the most abundant isotopes) 1567 (M+), 1530 (M+
–
Cl), 765 [RuClLLЈ]+. X-ray quality crystals were obtained by slow
evaporation of a CH2Cl2/Et2O (1:10 v/v) solution.
Synthesis of [RuCl2L{P(OEt)3}2] (6): P(OEt)3 (0.08 mL, 0.48 mmol)
was added to a solution of compound 2 (0.150 g, 0.12 mmol) in
toluene (20 mL). The mixture was heated under reflux for 1 h and
the solvent was removed under vacuum. Addition of Et2O gave a
pale yellow precipitate and this was filtered off, washed with Et2O
and dried under vacuum. Yield: 0.14 g (62%). C38H54Cl2O8P4Ru
1
(934.71): calcd. C 48.83, H 5.82; found C 49.05, H 5.85. H NMR
(CDCl3): δ = 0.90 (t, J = 7 Hz, 9 H, CH3), 1.22 (t, J = 7 Hz, 9 H,
CH3), 3.26 [m, 3 H, CH2 (LЈ)], 3.43 [m, 3 H, CH2 (LЈ) + 1 H, CH2
(L)], 3.98 [m, 1 H, CH2 (L)], 4.23 [m, 3 H, CH2 (LЈ)], 4.40 [m, 1
H, CH2 (L)], 4.46 [m, 3 H, CH2 (LЈ)], 5.67 [m, 1 H, CH2 (L)] ppm.
Synthesis of [Ru2(µ-Cl)2Cl2(L)2{L(O)}2] (3): Method (a): A solution
of compound 2 (0.150 g, 0.12 mmol) in toluene (20 mL) was added
to a solution of L (0.75 mL, 0.26 mmol) in toluene and the mixture
was heated under reflux for 1 h, cooled to room temperature and
the solvent removed under vacuum. Et2O was added to the residue
and the resulting yellow solid was filtered off, washed with Et2O
and dried under vacuum. Yield: 0.18 g (92%). Method (b): A mix-
ture of [RuCl2(DMSO)4] (0.5 g, 1.03 mmol) and a solution of L
(7.5 mL, 2.14 mmol) in toluene (20 mL) was heated under reflux
for 2 h with stirring. The solution was cooled to room temperature
and the solvent was removed under vacuum to give an oily residue.
Et2O (5 mL) was added and the resulting yellow solid was filtered
off. Compounds 7 and 8 were obtained from the filtrate (see below).
The solid was washed with Et2O and dried under vacuum. Yield:
31P{1H}NMR (CDCl3): δ = 97.8 (ddd, Jcis = 24, 48 Hz, Jtrans
=
544 Hz, P1), 122.0 (ddd, Jcis = 46, 64 Hz, Jtrans = 544 Hz, P4), 129.8
(ddd, Jcis = 47, 48, 64 Hz, P2), 150.7 (ddd, Jcis = 24, 46, 47 Hz,
P3) ppm. FAB+/MS: m/z (calculated for the most abundant iso-
topes) 899 (M+ – Cl), 733 [M+ – Cl – P(OEt)3]. X-ray quality crys-
tals were obtained by slow evaporation of a CH2Cl2/Et2O (1:10 v/
v) solution.
Synthesis of [RuCl2(L)(Ph2POPPh2)] (7) and [RuCl(CO)(L)-
(PPh2OCH2)] (8): From the ether solution obtained during the syn-
thesis of compound 3 [Method (b), see above], the solvent was re-
3038
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 3028–3040

New Dinuclear Face- and Edge-Sharing Bioctahedral Ru Compounds
FULL PAPER
moved under vacuum, and the residue was treated with MeOH to
give a yellow solid, which was washed with MeOH and dried under
vacuum. This solid was a mixture of compounds 7 and 8 and these
were separated by column chromatography using silica gel as the
stationary phase. Complex 7 was eluted first using a mixture of
CH2Cl2/Et2O (10:1, v:v). The eluent was removed under vacuum
and the residue was treated with EtOH to give a yellow solid, which
was filtered off, washed with EtOH and dried under vacuum. Yield:
L]+. X-ray quality crystals were obtained by slow evaporation of a
CH2Cl2/EtOH (1:10 v/v) solution.
CCDC-297717 to -297721 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Details of crystal data and structural refinement are given in
Table 9. The data were collected with a SIEMENS Smart CCD
area-detector diffractometer with graphite-monochromated Mo-Kα
radiation. Absorption correction was carried out using SAD-
ABS.[25]
1
0.012 g (12%). H NMR (CDCl3): δ = 4.30 (m, 4 H, CH2), 6.90–
7.50 (m, 40 H, Ph) ppm. 31P{1H} NMR (CDCl3): δ = 106.8 (m,
P3,4), 133.0 (m, P1,2) ppm. C50H44Cl2O3P4Ru (988.75): calcd. C
60.74, H 4.49; found C 60.60, H 4.50. FAB+/MS: m/z (calculated
for the most abundant isotopes) 988 (M+), 953 (M+ – Cl), 602
[RuCl2L]+. X-ray quality crystals were obtained by slow evapora-
tion of a CH2Cl2/EtOH (1:10 v/v) solution. Complex 8 was eluted
using CH2Cl2 as eluent. The solvent was removed under vacuum
and the residue was treated with EtOH. The resulting white solid
was filtered off, washed with EtOH and dried under vacuum. Yield:
0.013 g (1.5%). IR (KBr disc): 1953 (s) (νco) cm–1. 1H NMR
(CDCl3): δ = 3.80–4.80 (m, 6 H, CH2), 7.20–7.80 (m, 30 H, Ph)
ppm. 31P{1H} NMR (CDCl3): δ = 76.0 (dd, J12 = 341, J13 = 14 Hz,
P1), 131.5 (dd, J23 = 31 Hz, P3), 133.3 (dd, P2) ppm. C40H36ClO4-
P3Ru (810.15): calcd. C 59.30, H 4.48; found C 59.46, H 4.46.
FAB+/MS: m/z (calculated for the most abundant isotopes) 782
The structures of 5a and 8 were solved by Patterson methods and
the structures of 2a, 6 and 7 were solved by direct methods. All of
the structures were refined by a full-matrix least-squares based on
F2.[26] In the case of 5a and 7 the compounds crystallised with a
solvent molecule and the Squeeze program was used to correct the
reflection data for the diffuse scattering due to disordered sol-
vent.[27] Non-hydrogen atoms were refined with anisotropic dis-
placement parameters. Hydrogen atoms were included in idealised
positions and refined with isotropic displacement parameters.
Atomic scattering factors and anomalous dispersion corrections for
all atoms were taken from International Tables for X-ray Crystal-
(M+ – CO), 775 (M+ – Cl), 747 (M+ – CO – Cl), 595 [RuCl(CO)- lography.[28]
Table 9. Crystallographic data for 2a, 5a, 6, 7 and 8.
Compound
2a
5a
6
7
8
Empirical formula
Formula mass
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C54H54Cl4O5P4Ru2S C72H78Cl4O8P6Ru2 C38H54Cl2O8P4Ru
C50H44Cl2O3P4Ru
988.70
293(2)
0.71073
monoclinic
P21/c
18.2857(15)
10.9637(9)
23.896(2)
90
94.062(2)
90
4778.6(7)
4
1.374
C40H36ClO4P3Ru
810.12
293(2)
0.71073
monoclinic
P21/c
10.3989(19)
30.417(5)
14.4224(19)
90
125.777(9)
90
3701.0(10)
4
1.454
1282.85
293(2)
1601.10
293(2)
934.66
293(2)
0.71073
triclinic
P1
0.71073
triclinic
P1
0.71073
monoclinic
P21/c
¯
¯
13.089(2)
14.520(3)
19.143(3)
110.211(4)
93.650(4)
99.004(4)
3344.8(10)
2
12.312(4)
16.121(5)
24.310(7)
73.483(8)
81.195(6)
83.280(7)
4558(2)
19.068(4)
13.511(3)
17.006(4)
90
102.146(5)
90
γ [°]
Volume [Å3]
Z
4283.4(17)
4
2
Dcalcd [Mg/m3]
Absorption coefficient [mm–1
F(000)
1.274
1.167
1.449
]
0.776
0.596
0.688
0.614
2024
0.666
1656
1300
1640
1936
Crystal size [mm]
θ range for data collection [°]
Index ranges
0.24×0.14×0.09
1.52–28.11
–17 Յ h Յ 17
–19 Յ k Յ 19
–16 Յ l Յ 25
17668
0.29×0.214×0.23
1.68–28.19
–16 Յ h Յ 15
–21 Յ k Յ 13
–31 Յ l Յ 30
30329
0.34×0.21×0.20
1.86–28.07
–25 Յ h Յ 20
–16 Յ k Յ 17
–17 Յ l Յ 22
27353
0.50×0.33×0.26
1.71–28.03
–16 Յ h Յ 23
–13 Յ k Յ 14
–31 Յ l Յ 31
27535
0.25×0.27×0.15
1.34–28.08
–13 Յ h Յ 13
–40 Յ k Յ 25
–18 Յ l Յ 18
19695
Reflections collected
Independent reflections
12503
21088
10210
10879
8278
[R(int) = 0.0740]
3658
0.765
[R(int) = 0.1186]
3904
0.939
[R(int) = 0.1652]
3373
0.981
[R(int) = 0.0441]
6882
0.940
[R(int) = 0.1512]
2658
0.918
Reflections observed (Ͼ2σ)
Data completeness
Max. and min. transmission
1.00000 and
0.81992
12503/0/598
0.969
1.0000 and 0.7838
1.0000 and 0.711
1.00000 and
0.817076
10879/0/541
0.849
1.0000 and 0.36612
Data/restraints/parameters
Goodness-of-fit on F2
21088/0/833
0.608
10210/0/484
0.700
8278/0/450
0.811
Final R indices [I Ͼ 2σ(I)]
R1 = 0.0987
wR2 = 0.2866
R1 = 0.2550
wR2 = 0.3317
2.637/–0.637
R1 = 0.0724
wR2 = 0.1638
R1 = 0.2650
wR2 = 0.1992
0.632/–0.451
R1 = 0.0553
wR2 = 0.0699
R1 = 0.1974
wR2 = 0.0915
0.695/–1.054
R1 = 0.0386
wR2 = 0.0673
R1 = 0.0748
wR2 = 0.0728
0.509/–0.371
R1 = 0.0732
wR2 = 0.1231
R1 = 0.2516
wR2 = 0.1652
1.088/–0.617
R indices (all data)
Largest diff. peak/hole [e/Å3]
Eur. J. Inorg. Chem. 2006, 3028–3040
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3039

J. Bravo, S. García-Fontán et al.
FULL PAPER
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Acknowledgments
[14]
Financial support from the Xunta de Galicia (Project
PGIDT04PXIC31401PN) and from the Spanish Ministry of Edu-
cation and Science (Project BQU2003-06783) is gratefully acknowl-
edged. We thank the University of Vigo CACTI services for collect-
ing X-ray data and recording NMR spectra.
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Received: March 1, 2006
Published Online: June 6, 2006
3040
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 3028–3040