Synthesis and structural and spectroscopic characterization of new Ru II-dmso precursors with face-capping ligands for use in self-assembly reactions

Article abstract of DOI:10.1002/ejic.200400717

The aim of this work is the preparation of new, easy-to-make, octahedral Ru^II precursors with facial geometry to be used in self-assembly reactions. We chose dmso as a leaving group and 1,4,7-trithiacyclononane ([9]aneS₃), tris(pyrazolyl)methane [CH(pz)₃, pz = pyrazol-1-yl], or triphos [CH₃C(CH₂-PPh₂) ₃] as the face-capping ligand (fcl). We describe here the preparation and structural characterization of three new dicationic Ru^II complexes (as triflate salts) of the type fac-[Ru(fcl)(solv)₃] ²⁺, namely fac-[Ru([9]aneS₃)(dmso-O)(dmso-S) ₂]²⁺ (3b), which equilibrates in solution with the linkage isomer fac-[Ru([9]aneS₃)(dmso-O)₂(dmso-S)]²⁺ (3a), fac-[Ru{CH(pz)₃}(dmso-O)(dmso-S)₂]²⁺ (7), and fac-[Ru(triphos)(dmso-O)₂(H₂O)]²⁺ (9). In all cases the preferred synthetic procedure involved coordination of the face-capping ligand to cis-[RuCl₂(dmso)₄] first, followed by replacement of the chlorides with dmso (or water) molecules assisted by addition of AgCF₃SO₃ (AgOTf). NMR investigations showed that hydrolysis of the dmso ligands occurs very easily for 3 in water and for 9 in chloroform, while for complex 7 only the O-bound dmso ligand is replaced in water. In the course of this work, the following complexes were also isolated and structurally characterized: fac-[Ru([9]aneS₃)Cl(dmso-S) ₂][OTf] (2), trans,cis,cis-[RuCl₂(dmso-S) ₂{CH(pz)₂(pz)}] (4), trans,cis,cis-[RuCl ₂(dmso-S)₂(pzH)₂] (5), fac-[Ru{CH(pz) ₃}Cl₂(dmso-S)] (6), fac-[Ru([9]aneS₃)(py) ₃][OTf]₂ (11), fac-[Ru([9]aneS₃)(py) ₂-(CH₃CN)][OTf]₂ (13), and fac-[Ru([9]aneS ₃O)(dmso-O)₂(dmso-S)][OTf]₂ ([9]aneS ₃O = 1,4,7-trithiacyclononane 1-oxide); in 4 the tripodal tris(pyrazolyl)methane acts as a bidentate ligand. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Full text of DOI:10.1002/ejic.200400717

FULL PAPER
Synthesis and Structural and Spectroscopic Characterization of New RuII-dmso
Precursors with Face-Capping Ligands for Use in Self-Assembly Reactions
Elisabetta Iengo,[a] Ennio Zangrando,[a] Edi Baiutti,[a] Fabio Munini,[a] and Enzo Alessio*[a]
Keywords: Facial coordination / Ruthenium / Self-assembly / Tridentate ligands / Tripodal ligands
The aim of this work is the preparation of new, easy-to-make,
octahedral RuII precursors with facial geometry to be used in
self-assembly reactions. We chose dmso as a leaving group
and 1,4,7-trithiacyclononane ([9]aneS3), tris(pyrazolyl)meth-
ane [CH(pz)3, pz = pyrazol-1-yl], or triphos [CH3C(CH2-
PPh2)3] as the face-capping ligand (fcl). We describe here the
preparation and structural characterization of three new di-
cationic RuII complexes (as triflate salts) of the type fac-
of AgCF3SO3 (AgOTf). NMR investigations showed that hy-
drolysis of the dmso ligands occurs very easily for 3 in water
and for 9 in chloroform, while for complex 7 only the O-
bound dmso ligand is replaced in water. In the course of this
work, the following complexes were also isolated and struc-
turally characterized: fac-[Ru([9]aneS3)Cl(dmso-S)2][OTf] (2),
trans,cis,cis-[RuCl2(dmso-S)2{CH(pz)2(pz)}] (4), trans,cis,cis-
[RuCl2(dmso-S)2(pzH)2] (5), fac-[Ru{CH(pz)3}Cl2(dmso-S)]
(6), fac-[Ru([9]aneS3)(py)3][OTf]2 (11), fac-[Ru([9]aneS3)(py)2-
(CH3CN)][OTf]2 (13), and fac-[Ru([9]aneS3O)(dmso-O)2-
(dmso-S)][OTf]2 ([9]aneS3O = 1,4,7-trithiacyclononane 1-ox-
ide); in 4 the tripodal tris(pyrazolyl)methane acts as a biden-
tate ligand.
[Ru(fcl)(solv)3]2+, namely fac-[Ru([9]aneS3)(dmso-O)(dmso-S)
2+
]
(3b), which equilibrates in solution with the linkage iso-
2
mer
fac-[Ru([9]aneS3)(dmso-O)2(dmso-S)]2+
(3a), fac-
[Ru{CH(pz)3}(dmso-O)(dmso-S)2]2+ (7), and fac-[Ru(triphos)-
(dmso-O)2(H2O)]2+ (9). In all cases the preferred synthetic
procedure involved coordination of the face-capping ligand
to cis-[RuCl2(dmso)4] first, followed by replacement of the
chlorides with dmso (or water) molecules assisted by addition
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
semblies, the number of metal-containing components is
relatively limited. Most frequently used are the square-
Introduction
Metal-mediated synthetic procedures involving the self-
assembly of electron-donor building blocks (polytopic or-
ganic ligands) and electron-acceptor components (naked
ions or coordination compounds with some labile ligands)
are increasingly being exploited for the preparation of
stable, shape-persistent supramolecular assemblies of nano-
scopic dimensions.[1] Fascinating three-dimensional systems
have been reported by several groups.[2,3] Compared to na-
ked ions, in which the number of available coordination
sites for self-assembly and their geometry is determined by
the nature of the ion, the use of suitable coordination com-
pounds allows, in principle, a better control of the number
and geometry of such sites. In addition, useful properties
can be introduced into the supramolecular systems by the
nonparticipating ligands. Also, the solubility of the prod-
ucts can be largely influenced by the nature of the ancillary
ligands at the metal centers.
planar complexes [Pd(en)(ONO2)2] (en
= ethylenedi-
amine),[3e–3g,3k,4] [Pd(bipy)(ONO2)2] (both soluble in
water),[5] and [Pd(dppp)(OTf)2] [soluble in chlorinated sol-
vents, dppp = 1,2-bis(diphenylphosphanyl)propane, OTf =
CF3SO3, triflate],[3d,6] which yield cis bifunctional dicationic
metal fragments after dissociation of the two weakly coor-
dinated anions. Square-planar complexes with labile neutral
ligands, such as cis-[PtCl2(PhCN)2] and trans-
[PdCl2(PhCN)2], which yield the bifunctional metal frag-
ments cis-PtCl2 and trans-PdCl2, respectively, have also
been employed in self-assembly reactions.[7] The use of octa-
hedral coordination complexes is more rare and, in most
cases, concerns complexes such as [ReX(CO)5] (X = Cl, Br)
[8]
or trans-[RuCl2(dmso)2(L)2] (L = CO, dmso)[9] that yield
the cis bifunctional neutral fragments fac-ReX(CO)3 and
trans,cis-RuCl2(L)2, respectively.
Even though the two coordination sites available in these
metal fragments define a linear or planar geometry, 3D ad-
ducts have been obtained; tridimensionality can be induced
by flexible organic polytopic ligands or by a noncoplanar
mutual orientation of planar rigid fragments. In general, in
both cases, the shape of the 3D product is rarely predictable
a priori.
However, a literature survey shows that, while a large
number of polytopic organic ligands have been employed
for the construction of metal-mediated supramolecular as-
[a] Dipartimento di Scienze Chimiche, Università di Trieste,
Via L. Giorgieri 1, 34127 Trieste, Italy
E-mail: alessi@mail.univ.trieste.it
We believe that the field of coordination-driven self-as-
sembly would greatly benefit from the introduction of new,
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2005, 1019–1031
DOI: 10.1002/ejic.200400717
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E. Iengo, E. Zangrando, E. Baiutti, F. Munini, E. Alessio
FULL PAPER
easy-to-make, coordination compounds having three (or
more) readily available coordination sites for self-assembly.
In particular, we are interested in the development of low-
valent metal fragments with three sites in facial geometry
occupied by good leaving groups, either weak neutral li-
gands (e.g. solvent molecules) or weakly coordinating
anions. In such cases the tridimensionality of the adduct
would be inherently determined by that of the metal frag-
ment. The remaining three positions must be firmly held
by nonparticipating ligands, so that neither dissociation nor
isomerization occur during the substitution reaction with
the bridging building blocks. Thus, the three permanent fa-
cial atoms may be conveniently embedded in a face-capping
Scheme 1. Schematic representations of the RuII complexes with
face-capping ligands discussed in this work.
ligand (fcl), either
a
heterocycle,[10–12]
a
tripodal
ligand,[13,14] or an organometallic fragment such as η5-cy-
Results
clopentadienyl or η6-arene.[15]
The main ruthenium precursor used in this work is the
well known complex cis-[RuCl2(dmso)4]. Several examples
in the literature indicate that the reaction of cis-
[RuCl2(dmso)4] with one equivalent of a neutral, face-cap-
ping ligand usually leads to fac-[Ru(fcl)Cl2(dmso-S)] com-
plexes after replacement of three facial sulfoxides (one O-
bonded and two S-bonded).[18] Treatment of fac-[Ru(fcl)-
Cl2(dmso-S)] with two equivalents of a soluble silver salt,
such as AgOTf, in a weakly coordinating solvent (solv) is
expected to yield the desired fac-[Ru(fcl)(solv)3][OTf]2 com-
plexes.[11a,13,18] For example, the reaction of fac-[Ru([9]-
aneS3)Cl2(dmso-S)] (1) with AgOTf in refluxing acetonitrile
produces fac-[Ru([9]aneS3)(CH3CN)3][OTf]2 in excellent
yield.[11a]
Even though most of the low-valent, half-sandwich com-
plexes described in the literature were not specifically devel-
oped for use in self-assembly reactions (for example, they
have been widely investigated as homogeneous catalysts),[16]
there are some remarkable exceptions.[3a,12,17] For example,
RuII-, RhIII-, and IrIII-arene fragments have been exploited
as building blocks for the construction of supramolecular
cubes and metallamacrocyclic complexes.[3a,17] One striking
example with a nonorganometallic fragment is that of the
molecular cube [{Ru([9]aneS3)}8(μ-4,4Ј-bipy)12][OTf]16 ([9]
aneS3 = 1,4,7-trithiacyclononane), which is obtained by
treatment of fac-[Ru([9]aneS3)Cl2(dmso-S)] with the linear
ditopic ligand 4,4Ј-bipy in an 8:12 stoichiometry in nonco-
ordinating solvents. The fac-Ru([9]aneS3) and 4,4Ј-bipy
fragments form the corners and edges of the cube, respec-
tively.[12a] However, this synthetic procedure requires pro-
longed reaction times and heating (four weeks in nitrometh-
ane at refluxing temperature), and the addition of AgOTf to
remove chlorides. In an ideal metal-mediated self-assembly
process, two (or more) components are mixed in solution
in the appropriate ratio and react spontaneously with each
other to afford the desired product; external interventions,
such as addition of silver salts to remove coordinated ha-
lides and filtration of precipitates (other than the product),
should be avoided. Therefore, precursors with more-labile
leaving ligands, such as those mentioned above, would be
much preferred for self-assembly purposes.
As an alternative, in some cases we also employed the
dicationic precursor fac-[Ru(dmso-S)3(dmso-O)3][OTf]2. In
this synthetic approach removal of the chlorides from cis-
[RuCl2(dmso)4] occurred first and was followed by coordi-
nation of the face-capping ligand (see also Scheme 5).
Compounds with 1,4,7-Trithiacyclononane ([9]aneS3)
The complex fac-[Ru([9]aneS3)Cl2(dmso-S)] (1), despite
being an excellent precursor for inorganic synthesis,[11,12] is
not suitable as such for facial self-assembly reactions with
neutral, monodentate bridging ligands, as chloride replace-
In this work we report our results concerning the prepa-
ration of three new, easy-to-make [Ru(fcl)(solv)3][OTf]2
complexes {fcl = [9]aneS3, tris(pyrazolyl)methane [CH-(pz)
3, pz = pyrazol-1-yl], or triphos [CH3C(CH2PPh2)3]; solv
= dmso or H2O} (Scheme 1); dmso was chosen as, in our
experience with ruthenium precursors, it is normally a
better leaving group than the widely used CH3CN. The
three face-capping ligands were chosen with the aim of in-
vestigating a range of electronic, steric, and solubility prop-
erties; in addition, they are either commercially available or
very easily prepared and, unlike the organometallic frag-
ments, their reactions do not require the use of Schlenk
techniques. In the case of triphos, we partially revisited the
work of Venanzi and co-workers on the Ru/dmso/triphos
systems.[13]
Scheme 2.
1020
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RuII-dmso Precursors with Face-Capping Ligands
FULL PAPER
ment needs the assistance of Ag+.[12d–12f] For example, fac- excess of AgOTf in refluxing methanol in the presence of
[Ru([9]aneS3)(L)3][PF6]2 complexes (L = py or 4,4Ј-bipy) dmso (Scheme 2).
can be obtained by treatment of 1 with AgPF6 and a large
The IR spectrum of the product, which analyzed cor-
excess of ligand (L/Ru = in the range from 14 to 25) in rectly for [Ru([9]aneS3)(dmso)3][OTf]2 (3), showed the pres-
refluxing ethanol/water mixtures.[12b,12c]
ence of both S-bonded (S=O stretching at ν = 1088 cm–1)
˜
With the aim of preparing fac-[Ru([9]aneS3)(dmso)3]- and O-bonded (S=O stretching at ν = 933 and 914 cm–1)
˜
[OTf]2, we found that the reaction of 1 with two equivalents dmso molecules. The 1H NMR spectrum of 3 in noncoordi-
of AgOTf in refluxing acetone in the presence of dmso af- nating solvents (e.g. CD3NO2 or [D6]acetone), besides
forded a crystalline product (2) that, according to spectro- many, low-intensity multiplets for the [9]aneS3 protons be-
scopic investigations and X-ray diffraction analysis, was es- tween δ = 2.8 and 3.4 ppm, contains two sets of signals in
tablished to be the monocationic complex fac-[Ru([9]aneS3)- an approximate 2.5 to 1 ratio in the region of dmso reso-
Cl(dmso-S)2][OTf] (2) (Scheme 2, Figure 1).[19] The same nances; the most abundant has two singlets for dmso-O and
product was also obtained when the above reaction was per- one for dmso-S ligands, while the less abundant one has
formed in pure dmso at 100 °C.
one singlet for dmso-O and two for dmso-S ligands (Fig-
ure 2). These two sets were attributed to the linkage isomers
fac-[Ru([9]aneS3)(dmso-O)2(dmso-S)]2+ (3a) and fac-[Ru([9]-
aneS3)(dmso-O)(dmso-S)2]2+ (3b), respectively. In each iso-
mer there are two equivalent dmso ligands with diastereo-
topic methyl groups; accordingly, their NMR resonances
are slightly broader than that of the other dmso because of
the long-range coupling (4JH,H Ϸ 0.5 Hz).[20]
X-ray structural determinations performed on crystals
selected both from the raw material and from a sample
recrystallized from acetone (at room temperature, upon ad-
dition of diethyl ether) gave the same results: in both cases
the solid-state structure corresponded to fac-[Ru([9]-
aneS3)(dmso-O)(dmso-S)2][OTf]2 (3b), i.e. the less-abundant
isomer in solution (Figure 3).[21] It is noteworthy that the
Ru–S distance in 3btrans to dmso-O [2.298(1) Å] is shorter
than the values observed for the other S atoms of [9]aneS3
[mean value 2.352(1) Å].
Dissolution of the crystals in CD3NO2 or [D6]acetone
afforded the usual NMR spectrum, with the same ratio be-
tween 3a and 3b, thus suggesting that an equilibrium be-
tween the two linkage isomers occurs in solution. However,
saturation of the dmso resonances of one isomer did not
result in any appreciable transfer of saturation to those of
the other one, thus indicating that the equilibrium must be
quite slow on the NMR timescale. As progressive hydrolysis
Figure 1. Molecular structure of the cation of fac-[Ru([9]aneS3)-
Cl(dmso-S)2][OTf] (2) with thermal ellipsoids at the 40% prob-
ability level. Selected bond lengths [Å] and angles [°]: Ru–S(1)
2.313(1), Ru–S(2) 2.346(1), Ru–S(3) 2.351(1), Ru–S(4) 2.325(1),
Ru–S(5) 2.339(1), Ru–Cl(1) 2.420(1); S(2)–Ru–S(4) 174.69(3), S(3)–
Ru–S(5) 175.21(3), S(1)–Ru–Cl(1) 173.03(3).
Replacement of both chlorides of 1 with dmso molecules
was accomplished by performing the reaction with a slight
1
Figure 2. H NMR spectrum (CD3NO2) of the mixture of the two linkage isomers 3a and 3b; dmso singlets are labeled (see insert for
labeling scheme). The other small resonances belong to [9]aneS3 protons.
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E. Iengo, E. Zangrando, E. Baiutti, F. Munini, E. Alessio
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state IR spectrum indicated the presence of S-bonded dmso
1
exclusively. The H NMR spectrum of 4 in CDCl3 shows
two singlets for dmso-S, integrating for six protons each,
which is consistent with two geometries, each featuring a
bidentate coordination for the tris(pyrazolyl)methane,
CH(pz)2(pz): either trans,cis,cis-[RuCl2(dmso-S)2{CH(pz)2-
(pz)}]
or
cis,trans,cis-[RuCl2(dmso-S)2{CH(pz)2(pz)}]
(Scheme 3).[23] In the first hypothesis the two dmso-S li-
gands are equivalent but have diastereotopic methyls, while
in the second hypothesis the two trans dmso-S ligands have
enantiotopic methyl groups but are not equivalent as the
N2Cl2 plane is not a plane of symmetry for the complex.
Figure 3. Molecular structure of the cation of fac-[Ru([9]-
aneS3)(dmso-O)(dmso-S)2][OTf]2 (3b) with thermal ellipsoids at the
40% probability level. Selected bond lengths [Å] and angles [°]: Ru–
O(1) 2.169(3), Ru–S(1) 2.298(1), Ru–S(2) 2.350(1), Ru–S(3)
2.355(1), Ru–S(4) 2.326(1), Ru–S(5) 2.307(1); O(1)–Ru–S(1)
171.49(10), S(2)–Ru–S(4) 174.15(5), S(3)–Ru–S(5) 176.64(5).
Scheme 3. The two possible geometries of compound 4 that are
of coordinated dmso was observed (minutes), it was not
possible to perform a saturation-transfer experiment (and/
or line-shape analysis) above room temperature.
1
compatible with the observed H NMR spectrum.
A cis,cis,cis geometry can be excluded since four methyl
resonances for the two sulfoxides would be expected. The
trans,cis,cis-[RuCl2(dmso-S)2{CH(pz)2(pz)}] geometry was
eventually confirmed by an X-ray structural investigation
(Figure 4), which showed that the tris(pyrazolyl)methane in
4 indeed acts as a bidentate ligand, with a chelating angle
of 81.61(13)°.
We also found that the reaction of fac-[Ru(dmso-S)3-
(dmso-O)3][OTf]2 with one equivalent of [9]aneS3 in a
number of refluxing solvents (nitromethane, methanol,
chloroform, and chloroform/acetone mixtures) yielded only
mixtures of the unreacted precursor and of the fully substi-
tuted product [Ru([9]aneS3)2][OTf]2, identified by elemental
analysis and by comparison with the NMR spectrum re-
ported in the literature.[22]
1
The H NMR spectrum of fac-[Ru([9]aneS3)(dmso)3]2+
(mixture of the two isomers) in D2O showed that hydrolysis
of the dmso ligands occurs within minutes after dissolution
(the resonance of a species with one coordinated dmso-S, δ
= 3.31 ppm, that integrates for 1/3 of the free dmso appears
and remains unchanged for longer observation times, up to
2 days). Under the same conditions only very slow hydroly-
sis of acetonitrile from fac-[Ru([9]aneS3)(CH3CN)3]2+ was
observed (ca. 30% after one week at ambient temperature).
Compounds with Tris(pyrazolyl)methane [CH(pz)3]
The reaction of cis-[RuCl2(dmso)4] with tris(pyrazolyl)-
methane, CH(pz)3, has not been described so far. We found
that treatment of cis-[RuCl2(dmso)4] with one equivalent of
CH(pz)3 in refluxing methanol yielded a yellow precipitate
and large, deep-orange crystals. The mixture was found to
contain three products, 4–6, in approximately equimolar
amounts (NMR ratio measured in [D6]DMSO, in which the
mixture is well soluble), which were separated and obtained
in pure form (see Experimental Section).
Figure 4. Molecular structure of trans,cis,cis-[RuCl2(dmso-S)2-
{CH(pz)2(pz)}] (4) with thermal ellipsoids at the 40% probability
level. Selected bond lengths [Å] and angles [°]: Ru–N(1) 2.119(3),
Ru–N(2) 2.148(4), Ru–S(1) 2.278(1), Ru–S(2) 2.262(1), Ru–Cl(1)
2.402(1), Ru–Cl(2) 2.416(1); N(1)–Ru–N(2) 81.61(13), N(1)–Ru–
S(1) 173.84(10), N(2)–Ru–S(2) 176.01(9), Cl(1)–Ru–Cl(2)
The elemental analysis of compound 4 was consistent
with the formula [RuCl2(dmso)2CH(pz)3], and the solid- 179.04(5).
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RuII-dmso Precursors with Face-Capping Ligands
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Complex 4 was also selectively prepared in good yield by confirmed this hypothesis, indicating that the molecular
reaction of trans-[RuCl2(dmso-S)4] with one equivalent of structure of 5 is trans,cis,cis-[RuCl2(dmso-S)2(pzH)2] (see
CH(pz)3 in chloroform at ambient temperature. It is in fact Supporting Information). Complex 5, which had been al-
well known that trans-[RuCl2(dmso-S)4] replaces two cis ready prepared by Taqui Khan and co-workers by treat-
dmso-S ligands to affording the trans,cis-RuCl2(dmso-S)2 ment of cis-[RuCl2(dmso)4] with two equivalents of pyr
fragment selectively.[24]
azole in acetonitrile at 60 °C,[25] is structurally similar to 4,
The 1H NMR spectrum of 5 in CDCl3 is very simple (see as it contains two cis pyrazole ligands instead of the two cis
Experimental Section), suggesting that the complex must be pyrazole units belonging to CH(pz)3 found in 4.
highly symmetrical and that, most likely, simple pyrazole
Elemental analysis of the third product, 6, suggested an
ligands (pzH), derived from the decomposition of tris(pyr- [RuCl2(dmso)CH(pz)3] stoichiometry. The pattern of the
1
azolyl)methane, are bound to ruthenium. X-ray analysis downfield region of the H NMR spectrum of 6 in nonco-
ordinating solvents (CD3NO2) is similar to that of complex
4, as it shows two sets of pyrazole resonances with a 2:1
intensity ratio and a singlet at δ = 8.87 ppm for the CH
proton of tris(pyrazolyl)methane. The region of the dmso
resonances contains one singlet for dmso-S (δ = 3.41 ppm),
integrating for six protons. The NMR spectrum of 6 is thus
consistent with a fac-[Ru{CH(pz)3}Cl2(dmso-S)] geometry
in which the two pz units trans to the chlorides are equiva-
lent and the methyl groups of dmso-S are enantiotopic.
This geometry was confirmed by an X-ray investigation
(Figure 5).
As anticipated in the Introduction, complex 6 is the pro-
duct expected from the reaction of cis-[RuCl2(dmso)4] with
one equivalent of a face-capping ligand. We found that
compound 6 can also be obtained in almost pure form and
in good yield by performing the reaction between cis-
[RuCl2(dmso)4] and CH(pz)3 at slightly higher temperature
(in refluxing ethanol rather than methanol), as the product
precipitates spontaneously from the reaction mixture. The
reactivity of cis-[RuCl2(dmso)4] towards CH(pz)3 is summa-
rized in Scheme 4.
Treatment of 6 with two equivalents of AgOTf in re-
fluxing methanol in the presence of dmso afforded fac-
[Ru{CH(pz)3}(dmso-O)(dmso-S)2][OTf]2 (7; Scheme 5).
The IR spectrum of 7 clearly indicates the presence of both
Figure 5. Molecular structure of fac-[Ru{CH(pz)3}Cl2(dmso-S)] (6)
with thermal ellipsoids at the 40% probability level. Selected bond
lengths [Å] and angles [°]: Ru–N(1) 2.052(9), Ru–N(2) 2.049(11),
Ru–N(3) 2.078(10), Ru–S(1) 2.251(4), Ru–Cl(1) 2.419(3), Ru–Cl(2)
2.406(3); N(1)–Ru–N(2) 87.8(4), N(1)–Ru–N(3) 84.4(4), N(2)–Ru–
N(3) 83.3(4), N(1)–Ru–Cl(1) 174.8(4), N(2)–Ru–Cl(2) 172.4(3),
N(3)–Ru–S(1) 177.1(3).
Scheme 4.
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S-bonded (S–O stretching at ν = 1155 cm–1) and O-bonded
˜
(S–O stretching at ν = 938 cm–1) dmso ligands. Its 1H NMR
˜
spectrum in noncoordinating solvents ([D6]acetone or
CD3NO2) shows three singlets for the dmso ligands, inte-
grating for six protons each, one O-bonded and two S-
bonded; the resonances for coordinated CH(pz)3 consist of
two sets of pyrazole protons with a 2:1 intensity ratio and
a singlet for the CH proton. X-ray diffraction studies con-
firmed the molecular structure of complex 7 (Figure 6); the
two equivalent dmso-S ligands have diastereotopic methyl
groups, which are responsible for the two NMR resonances
in the dmso-S region.
Figure 6. Molecular structure of the cation of fac-[Ru{CH(pz)3}-
(dmso-O)(dmso-S)2][OTf]2 (7) with thermal ellipsoids at the 40%
probability level. Selected bond lengths [Å] and angles [°]: Ru–N(1)
2.130(5), Ru–N(2) 2.123(4), Ru–N(3) 2.051(4), Ru–S(1) 2.272(2),
Ru–S(2) 2.283(2), Ru–O(3) 2.110(4); N(1)–Ru–N(2) 81.89(17),
N(1)–Ru–N(3) 86.70(18), N(2)–Ru–N(3) 85.42(17), N(3)–Ru–O(3)
174.32(18), N(1)–Ru–S(1) 175.61(12), N(2)–Ru–S(2) 169.52(13).
the dmso-O in fac-[Ru{CH(pz)3}(dmso-O)(dmso-S)2][OTf]2
(7).
The different binding mode of CH(pz)3 in 4 (bidentate)
compared to 6 and 7 (tripodal) is reflected in the values of
the Ru–N–N and Ru–N–C bond angles. Those found in 4
(131.0° and 123.6°, respectively) are quite different from
those found in 6 and 7 (mean values of 136.6° and 118.0°,
respectively).
Scheme 5.
When 7 was dissolved in D2O the O-bonded dmso was
rapidly and completely hydrolyzed as, in this solvent, the
dmso-O resonance was replaced by the signal of free dmso
at δ = 2.72 ppm; hydrolysis of the dmso-S ligands was not
observed. In addition, in D2O the resonance of the CH pro-
ton of coordinated CH(pz)3 decreased rather rapidly (min-
utes) because of exchange with the deuterated solvent. This
result suggests that, as might be expected, the acidity of this
Compounds with CH3C(CH2PPh2)3 (triphos)
We reinvestigated the reaction between cis-[RuCl2-(dmso)4]
proton in 7 is greater than in the neutral precursor 6, for and CH3C(CH2PPh2)3 with the aim of obtaining a more
which this phenomenon was not observed.
detailed characterization of the fac-[Ru(triphos)(dmso)3]2+
As an alternative, complex 7 was also obtained by reac- and fac-[Ru(triphos)(dmso)2(H2O)]2+ complexes described
tion of fac-[Ru(dmso-S)3(dmso-O)3][OTf]2 with one equiva- by Venanzi and co-workers.[13] Initially, we found that the
lent of CH(pz)3 in refluxing methanol (Scheme 5). In this reaction of cis-[RuCl2(dmso)4] with one equivalent of
case, unlike with [9]aneS3 (see above), we found no evidence triphos, even when performed under milder conditions than
of the formation of the homoleptic sandwich adduct fac- those reported in the literature (4 h in refluxing chloroform
[Ru{CH(pz)3}2][OTf]2.
vs. 24 h in refluxing toluene),[13] led to the isolation of the
The structural characterizations indicated that the metal dinuclear species [(triphos)Ru(μ-Cl)3Ru(triphos)]Cl (8) ex-
in complexes 4–7 displays a distorted octahedral geometry clusively (Scheme 6). Formation of the mononuclear com-
with coordination bond lengths falling in a range already plex fac-[RuCl2(triphos)(dmso-S)] was not observed. Then,
observed for similar ruthenium species.[26] Interestingly, the we found that treatment of 8 with four equivalents of Ag-
mean Ru–N bond length found in fac-[Ru{CH(pz)3}- OTf in refluxing methanol in the presence of dmso led ex-
Cl2(dmso-S)] (6) is shorter (by about 0.1 Å) than those clusively to the isolation of crystalline fac-[Ru(tri-
found in the other structures, but similar to that trans to phos)(dmso-O)2(H2O)][OTf]2 (9) in good yield (Scheme 6).
1024
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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RuII-dmso Precursors with Face-Capping Ligands
FULL PAPER
Figure 7. Molecular structure of the cation of fac-[Ru(tri-
phos)(dmso-O)2(H2O)][OTf]2 (9) with thermal ellipsoids the 40%
probability level. For the sake of clarity the phenyl carbon atoms
are indicated as spheres of fixed radius. Selected bond lengths [Å]
and angles [°]: Ru–O(1) 2.215(4), Ru–O(2) 2.190(4), Ru–O(3)
2.197(4), Ru–P(1) 2.272(2), Ru–P(2) 2.296(2), Ru–P(3) 2.280(2);
O(1)–Ru–P(1) 173.25(12), O(2)–Ru–P(2) 172.80(12), O(3)–Ru–P(3)
174.41(12).
Scheme 6.
Reactivity of the New Precursors
The reactivity of the new precursors with facial geome-
try, 3, 7 and 9, is currently being investigated in our labora-
tory and will be the subject of a subsequent paper. We re-
port here only one example concerning the reactivity of the
[9]aneS3 complex 3 towards the model ligand pyridine.
The reaction between 3 and a slight excess of pyridine
(py/Ru = 4) in refluxing methanol led selectively to the iso-
lation of fac-[Ru([9]aneS3)(py)3][OTf]2 (11) in excellent yield
(Scheme 7). As expected from literature data,[12d–12f] reac-
tion of 1 with pyridine under the same conditions did not
yield complex 11. By comparison, we found that the reac-
tion between the known acetonitrile-containing precursor
fac-[Ru([9]aneS3)(CH3CN)3][OTf]2 (12) and pyridine, de-
spite being performed at higher temperature (refluxing eth-
anol) and with a larger excess of ligand (py/Ru = 8), always
led to mixtures of 11 and of the disubstituted species fac-
[Ru([9]aneS3)(py)2(CH3CN)][OTf]2 (13; Scheme 7); both
The molecular structure of 9 was determined by X-ray
analysis (Figure 7). The dimensions of the triphos ligand
reflect a small degree of geometrical distortions, with Ru–
P distances of 2.272(2), 2.296(2), 2.280(2) Å (the latter trans
to the aqua ligand), and P–Ru–P bond angles that average
87.4°. Overall, the structural parameters of the tripodal li-
gand are very similar to those found in the dinuclear com-
plex cation [(triphos)Ru(μ-Cl)3Ru(triphos)]+.[13]
We found no evidence of the formation of fac-[Ru(tri-
phos)(dmso-O)3][OTf]2 (10); compound 9 was the only pro-
duct that we isolated, even under the conditions (dmso at
110 °C) that, according to the literature,[13] should afford
10. Our synthetic procedure leading to 9 is simpler than
that described by Venanzi and co-workers[13] in that it avo-
ids the tedious removal of dmso. Several attempts to pre-
pare either 9 or 10 by reaction of fac-[Ru(dmso-S)3(dmso-
O)3][OTf]2 with triphos in a number of refluxing solvents
(e.g. acetone, methanol, toluene) were unsuccessful and led
to the isolation of small amounts of unreacted precursor
only.
Complex 9 was found to be insoluble in water but soluble
in a range of organic solvents, including chloroform. The
1H NMR spectrum of 9 in CDCl3 shows, besides the reso-
nances of coordinated triphos, only the singlet of free dmso
at δ = 2.62 ppm, thus indicating that both dmso-O ligands
are rapidly released and probably replaced by water mole-
cules. The 31P NMR spectrum shows a singlet at δ =
38.2 ppm, in agreement with the equivalence of the three P
atoms in the hydrolyzed species.
Scheme 7. For simplicity, in 3a and 3b O = dmso-O and S =dmso-
S.
Eur. J. Inorg. Chem. 2005, 1019–1031
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E. Iengo, E. Zangrando, E. Baiutti, F. Munini, E. Alessio
FULL PAPER
products were isolated in pure form and characterized spec- distances in 3b compared to 7 might be found in the greater
troscopically and by X-ray diffraction analysis (see Sup- trans influence of trithiacyclononane than tris(pyrazolyl)-
porting Information).[27]
methane. This consideration might also explain why the S/
Thus, owing to the greater lability of dmso than acetoni- O linkage isomerization of one sulfoxide was observed for
trile bound to the Ru([9]aneS3)2+ fragment (see above), the trithiacyclononane complex 3, but not in the case of the
complex 3 proved to be a better precursor than 12 in reac- corresponding tris(pyrazolyl)methane complex 7.
tions involving the selective replacement of all three leaving
groups with monodentate ligands.
As the new complexes were prepared with the aim of
being employed in self-assembly reactions, the lability of the
coordinated dmso molecules is an important parameter to
be assessed. NMR investigations showed that hydrolysis of
the dmso ligands occurred very easily from 3 in waterand
from 9 in chloroform. In the case of complex 7, only the O-
Discussion and Conclusions
In summary, we have prepared and structurally charac- bound dmso ligand was found to be replaced in water. In
terized three new, easy-to-make, complexes of the type fac- general, the lability of the dmso ligands of the three dicat-
[Ru(fcl)(solv)3][OTf]2, namely fac-[Ru([9]aneS3)(dmso-O)- ionic precursors reflects the trend of Ru–dmso bond dis-
(dmso-S)2][OTf]2 (3b), which equilibrates in solution of tances. In addition, NMR investigations of the two similar
noncoordinating solvents with the linkage isomer fac- complexes fac-[Ru([9]aneS3)(dmso)3]2+ (3) and fac-[Ru([9]-
[Ru([9]aneS3)(dmso-O)2(dmso-S)]2+ (3a), fac-[Ru{CH(pz)3}- aneS3)(CH3CN)3]2+ (12) in coordinating solvents such as
(dmso-O)(dmso-S)2][OTf]2 (7), and fac-[Ru(triphos)(dmso- water have shown that coordinated dmso is much more la-
O)2(H2O)][OTf]2 (9). In all cases the preferred synthetic bile than acetonitrile. Accordingly, replacement of the three
procedure involves coordination of the face-capping ligand dmso ligands of 3 with pyridine occurs more easily than
to cis-[RuCl2(dmso)4] first, followed by replacement of chlo- that of the acetonitrile ligands of 12.
rides with dmso (or water) molecules assisted by addition
In conclusion, a number of experimental results (total
of AgOTf. The isolated yields of compounds 3 and 9 were yield, structural considerations in the solid state, the lability
satisfactory {ca. 80% for 3, and ca. 50% for 9, both calcu- of the dmso ligands in solution, preliminary results on the
lated with respect to cis-[RuCl2(dmso)4]}, while that of 7 reactivity towards model ligands) agree that fac-[Ru([9]-
was quite low (18–24% depending on the synthetic route). aneS3)(dmso)3][OTf]2 (3) and fac-[Ru(triphos)(dmso-O)2-
In addition, unlike [9]aneS3 and triphos, tris(pyrazolyl)- (H2O)][OTf]2 (9) are the most promising complexes for fur-
methane is not commercially available and it is the only fcl, ther use in self-assembly reactions with polytopic ligands.
among the three tested, that undergoes decomposition Their solubility, a fundamental parameter to be considered
rather easily and shows a tendency to coordinate in a biden- in self-assembly reactions, is strongly influenced by the nat-
tate rather than a tridentate manner.
ure of the face-capping ligand. Taken together, they cover
It should be noted that while in the dications 3b and 7 a broad range of solvents: while both complexes are soluble
there are two S-bonded and one O-bonded dmso ligands, in nitromethane, acetone and methanol, 3 is also well solu-
in 9 both dmso ligands are bonded through oxygen and, ble in water, while 9 is soluble in chloroform.
according to Venanzi and co-workers,[13] the third one also
It may be argued that the steric demand of triphos in 9
binds in the same manner when it replaces the water mole- might disfavor coordination of bulkier ligands in place of
cule to give 10. The preferential O-bonding of dmso in 9 the dmso and water molecules; however, the steric bulk of
might be due to both steric and electronic reasons: the steric dppp, which may be considered as the bidentate analog of
bulk of the phenyl groups of coordinated triphos might triphos, has not prevented the use of Pd(dppp)2+ and
favor coordination of dmso through oxygen, as dmso-O is Pt(dppp)2+ fragments in the construction of many 2D and
less sterically demanding than dmso-S. In addition, dmso 3D supramolecular adducts through self-assembly pro-
might coordinate through oxygen to avoid competition for cedures.[3d,6]
π-electrons with the trans phosphane, as is already well es-
tablished for the coordination of dmso trans to other strong
π-accepting ligands such as CO and NO.[18]
Experimental Section
A comparison of the structural data of the dmso ligands
in the three dicationic species fac-[Ru([9]aneS3)(dmso-S)2- Infrared spectra (KBr) were obtained on a Perkin–Elmer 2000 NIR
1
FT-Raman spectrometer. H and 31P{1H} NMR spectra were col-
lected at room temperature at 400 and 161.9 MHz, respectively, on
a Jeol Eclipse 400 FT spectrometer, with 2,2-dimethyl-2,2-silapen-
tane-5-sulfonate (DSS) as an internal standard for D2O solutions
and the residual non-deuterated solvent signal as reference for spec-
tra recorded from [D6]acetone (δ = 2.04 ppm), CD3NO2 (δ =
4.33 ppm), and CDCl3 (δ = 7.26 ppm) solutions. 31P NMR spectra
were referenced to external H3PO4 set at δ = 0 ppm. ES-MSdata
were obtained on a Perkin–Elmer AP1 spectrometer. Samples were
dissolved in acetonitrile; the spectra were recorded in the positive-
(dmso-O)]2+ (3b), fac-[Ru{CH(pz)3}(dmso-O)(dmso-S)2]2+
(7), and fac-[Ru(triphos)(dmso-O)2(H2O)]2+ (9) shows the
following trend for Ru–O(dmso) distances: trans to N
[2.110(4) Å in 7] Ͻ trans to S [2.169(3) Å in 3b] Ͻ trans to P
[2.202(4) Å, mean value in 9]. In addition, the Ru–S(dmso)
bonds trans to pyrazole N atoms in 7 are also significantly
shorter (0.04 Å) than the corresponding bonds trans to the
S atoms in 3b. As both coordinated CH(pz)3 and [9]aneS3
have a small steric bulk in the region of space occupied by
the dmso ligands, the reason for the longer Ru–dmso bond ion mode at 5.6 kV accelerating potential. Elemental analyses were
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RuII-dmso Precursors with Face-Capping Ligands
FULL PAPER
performed at the Dipartimento di Scienze Chimiche, University of
Trieste.
by filtration, washed with diethyl ether, and vacuum dried (yield:
0.15 g). The mixture was found to contain approximately equi-
molar amounts of 4, 5, and 6 by NMR spectroscopy. The orange
crystals of 4 were manually separated under a microscope, washed
with cold methanol and diethyl ether, and vacuum dried.
C14H22N6Cl2O2RuS2 (542.46): calcd. C 31.0, H 4.09, N 15.49;
Trithiacyclononane, triphos, and deuterated solvents were pur-
chased from Aldrich and used as received. Tris(pyrazolyl)meth-
ane,[28]fac-[Ru([9]aneS3)(CH3CN)3][OTf]2 (12),[11a] fac-[Ru([9]-
aneS3)Cl2(dmso-S)] (1),[11a]cis-[RuCl2(dmso)4],[29] and trans-
[RuCl2(dmso)4][29] were prepared as described in the literature. fac-
[Ru(dmso-O)3(dmso-S)3][OTf]2 was prepared by an improved
method compared to those reported in the literature for similar fac-
[Ru(dmso-O)3(dmso-S)3][X]2 (X = ClO4, BF4) compounds:[30,31]cis-
[RuCl2(dmso)4] (0.48 g, 1 mmol) was treated with a slight excess of
AgOTf in refluxing toluene in the presence of dmso (dmso/Ru =
4) for 30 min; the precipitate was extracted with methanol. Solvent
removal afforded the product, which was recrystallized from ace-
tone upon addition of diethyl ether. Yield: 0.6 g (70%).
found C 31.4, H 4.01 N 15.23. Selected IR (Nujol): ν = 1086 (s,
˜
νSO dmso-S), 424 (w, νRu–S), 341 cm–1 (m, νRu–Cl). 1H NMR
(400 MHz, CDCl3, 25 °C): δ = 3.45 (s, 6 H, dmso-S), 3.47 (s, 6 H,
dmso-S), 6.39 (m, 2 H, H4 bound pz), 6.60 (m, 1 H, H4 unbound
pz), 7.79 (m, 2 H, H5 bound pz), 8.03 (m, 2 H, H3 + H5 unbound
pz), 8.26 (m, 2 H, H3 bound pz), 10.97 (s, 1 H, CH) ppm.
The remaining yellow solid, according to 1H NMR analysis, was a
mixture of 5 and 6 (and some residual 4). Treatment of the mixture
with chloroform (twice 5 mL) afforded a small amount of almost
pure 6 as an insoluble solid residue (see below). Diffusion of diethyl
ether into the chloroform solution afforded yellow crystals of 5.
C10H20N4Cl2O2RuS2 (464.39): calcd. C 25.8, H 4.34, N 12.06;
found C 25.3, H 4.18, N 12.02. 1H NMR (400 MHz, CDCl3,
25 °C): δ = 3.21 (s, 12 H, dmso-S), 6.38 (m, 2 H, H4 pzH), 7.63
(m, 2 H, H5 pzH), 7.98 (m, 2 H, H3 pzH), 12.6 (br. s, 2 H, NH
pzH) ppm.
fac-[Ru([9]aneS3)Cl(dmso-S)2][OTf] (2): fac-[Ru([9]aneS3)Cl2(dmso-
S)] (1; 0.18 g, 0.41 mmol) was dissolved in acetone (10 mL); dmso
(75 μL, 1 mmol) and AgOTf (0.21 g, 0.82 mmol) were added and
the light-protected mixture was heated to reflux for 1 h. After re-
moval of AgCl by filtration through fine paper, the yellow solution
was concentrated in vacuo to ca. 3 mL and stored at room tempera-
ture after dropwise addition of diethyl ether until saturation. A
light-yellow precipitate formed within 24 h and was removed by
filtration, washed with diethyl ether, and vacuum dried. Yield:
55 mg (20%). C11H24ClF3O5RuS6 (622.19): calcd. C 21.2, H 3.88;
trans,cis,cis-[RuCl2(dmso-S)2{CH(pz)2(pz)}] (4): As an alternative,
complex 4 was selectively prepared in good yield by the following
route: trans-[RuCl2(dmso-S)4] (0.1 g, 0.2 mmol) was dissolved in
CHCl3 (20 mL) and CH(pz)3 (45 mg, 0.21 mmol) was added. After
standing 24 h at room temperature, the resulting orange solution
was concentrated in vacuo to ca. 5 mL and stored at room tempera-
ture after dropwise addition of diethyl ether until saturation.
Orange crystals formed within 24 h and were removed by filtration,
washed with diethyl ether, and vacuum dried. Yield: 65 mg (60%).
See above for elemental analysis and spectroscopic characteriza-
tion.
found C 21.6, H 3.63. Selected IR (Nujol): ν = 1093 (s, νSO dmso-
˜
S), 428 cm–1 (w, νRu–S). 1H NMR (400 MHz, D2O, 25 °C): δ =
3.3–2.8 (m, 12 H, [9]aneS3), 3.38 (s, 6 H, dmso-S), 3.46 (s, 6 H,
1
dmso-S) ppm. H NMR (400 MHz, CD3NO2, 25 °C): δ = 3.3–2.8
(m, 12 H, [9]aneS3), 3.29 (s, 6 H, dmso-S), 3.38 (s, 6 H, dmso-S)
ppm.
Crystals suitable for X-ray diffraction were obtained by diffusion
of diethyl ether into an acetone solution of 2.
fac-[Ru{CH(pz)3}Cl2(dmso-S)] (6): cis-[RuCl2(dmso)4] (0.30 g,
0.62 mmol) was partially dissolved in absolute EtOH (20 mL);
CH(pz)3 (0.14 g, 0.62 mmol) was added and the mixture was heated
to reflux for 2 h. A yellow precipitate formed from the hot orange
solution. After cooling the mixture to room temperature, it was
removed by filtration, washed with cold ethanol and diethyl ether,
and vacuum dried. Yield: 0.13 g (45%). Concentration of the
mother liquor and addition of diethyl ether afforded a further yel-
low precipitate that, according to 1H NMR spectroscopy, was a
mixture of 5 and 6. Recrystallization: the product was dissolved in
the minimum amount of dmso (e.g. 0.15 g of 6 in 0.5 mL dmso),
the solution was diluted with acetone (5 mL) and diethyl ether was
added dropwise until saturation. Crystals of 6 suitable for X-ray
diffraction were obtained by diffusion of diethyl ether into the
dmso/acetone solution. C12H16N6Cl2ORuS (464.33): calcd. C 31.0,
H 3.47, N 18.09; found C 30.9, H 3.37, N 17.85. Selected IR (Nu-
fac-[Ru([9]aneS3)(dmso)3][OTf]2 (3): fac-[Ru([9]aneS3)Cl2(dmso-S)]
(1; 0.43 g, 1 mmol) was partially dissolved in MeOH (10 mL); dmso
(250 μL, 3.5 mmol) and AgOTf (0.60 g, 2.3 mmol) were added and
the light-protected mixture was heated to reflux for 3 h. After re-
moval of AgCl by filtration, the yellow solution was concentrated
in vacuo to ca. 5 mL. A yellow crystalline precipitate was obtained
within 24 h from the solution stored at room temperature after
dropwise addition of diethyl ether until saturation. It was removed
by filtration, washed with diethyl ether, and vacuum dried. Yield:
0.71 g (88%). C14H30F6O9RuS8 (813.93): calcd. C 20.6, H 3.71;
found C 20.7, H 3.77. Selected IR (Nujol): ν = 1088 (s, νSO dmso-
˜
S), 933 and 914 (s, νSO dmso-O), 517 (w, νRu–O), 418 cm–1 (w,
νRu–S). 1H NMR (400 MHz, CD3NO2, 25 °C): δ = 2.94 (s, 6 H,
dmso-O 3a), 2.96 (s, 6 H, dmso-O 3a), 3.04 (s, 6 H, dmso-O 3b),
3.18 (s, 6 H, dmso-S 3a), 3.34 (s, 6 H, dmso-S 3b), 3.43 (s, 6 H,
dmso-S 3b), 3.4–2.8 (m, 12 H, [9]aneS3) ppm. 1H NMR (400 MHz,
[D6]acetone, 25 °C): δ = 3.03 (s, 6 H, dmso-O 3a), 3.04 (s, 6 H,
dmso-O 3a), 3.13 (s, 6 H, dmso-O 3b), 3.22 (s, 6 H, dmso-S 3a),
3.42 (s, 6 H, dmso-S 3b), 3.49 (s, 6 H, dmso-S 3b), 3.5–2.7 (m, 12
H, [9]aneS3) ppm. Recrystallization: the product was dissolved in
acetone and then diethyl ether was added dropwise until saturation.
jol): ν = 1078 (s, νSO dmso-S), 424 cm–1 (w, νRu–S). 1H NMR
˜
(400 MHz, D2O, 25 °C): δ = 3.49 (s, 6 H, dmso-S), 6.56 (m, 2 H,
H4), 6.65 (m, 1 H, H4), 8.01 (m, 2 H, H5), 8.23 (m, 1 H, H5), 8.36
1
(m, 2 H, H3), 8.40 (m, 1 H, H3), 9.47 (s, 1 H, CH) ppm. H NMR
(400 MHz, CD3NO2, 25 °C): δ = 3.41 (s, 6 H, dmso-S), 6.49 (m, 2
H, H4), 6.60 (m, 1 H, H4), 8.07 (m, 2 H, H5), 8.23 (m, 1 H, H5),
8.28 (m, 2 H, H3), 8.31 (m, 1 H, H3), 8.87 (s, 1 H, CH) ppm.
trans,cis,cis-[RuCl2(dmso-S)2{CH(pz)2(pz)}] (4) and trans,cis,cis-
[RuCl2(dmso-S)2(pzH)2] (5): cis-[RuCl2(dmso)4] (0.20 g, 0.41 mmol)
was partially dissolved in MeOH (15 mL); CH(pz)3 (0.09 g,
0.41 mmol) was added and the mixture was heated to reflux for
2 h. The resulting orange solution was concentrated in vacuo to ca.
2 mL and stored at room temperature after dropwise addition of
diethyl ether until saturation. A yellow microcrystalline precipitate
containing big orange crystals formed within 12 h. It was removed
fac-[Ru{CH(pz)3}(dmso-O)(dmso-S)2][OTf]2 (7): This complex was
prepared by two different routes: a) by treatment of 6 with two
equivalents of AgOTf in the presence of dmso; b) by reaction of
fac-[Ru(dmso-S)3(dmso-O)3][OTf]2 with CH(pz)3. The yield of 7
with respect to the common precursor cis-[RuCl2(dmso)4] is similar
in the two procedures: 18% via route a, and 24% via route b.
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FULL PAPER
Route a: fac-[Ru{CH(pz)3}Cl2(dmso-S)] (6; 0.10 g, 0.21 mmol) was
dissolved in MeOH (5 mL); dmso (46 μL, 0.65 mmol) and AgOTf
(0.11 g, 0.43 mmol) were added and the light-protected mixture was
heated to reflux for 3 h. After removal of AgCl by filtration, the
yellow solution was concentrated in vacuo to ca. 2 mL and stored
at room temperature after dropwise addition of diethyl ether until
H, m-Ph), 7.27 (m, 18 H, o+p-Ph) ppm. 31P{1H} NMR
(161.9 MHz, CDCl3, 25 °C): δ = 38.2 ppm.
fac-[Ru([9]aneS3)(py)3][OTf]2 (11) and fac-[Ru([9]aneS3)(py)2-
(CH3CN)][OTf]2 (13): fac-[Ru([9]aneS3)(CH3CN)3][OTf]2 (12; 0.1 g,
0.14 mmol) was partially dissolved in EtOH (20 mL); pyridine
(92 μL, 1.13 mmol) was added and the mixture was heated to reflux
for 4 h. The resulting yellow-green solution was filtered through
fine paper to remove a small amount of a dark precipitate and then
concentrated in vacuo to ca. 2 mL and stored at room temperature
after dropwise addition of diethyl ether until saturation. A yellow
crystalline precipitate containing two types of crystals (big prisms
and small needles) formed within 24 h and was then removed by
filtration, washed with chloroform and diethyl ether, and vacuum
dried (yield 80 mg). The precipitate was shown to be an approxi-
mate 1:3 mixture of 11 and 13 by 1H NMR spectroscopy. The large
yellow prisms were manually separated from the mixture under a
saturation.
A pale-yellow microcrystalline precipitate formed
within 24 h and was removed by filtration, washed with diethyl
ether, and vacuum dried. Yield: 72 mg (40%). C18H28N6F6O9RuS5
(847.82): calcd. C 25.5, H 3.33, N 9.91; found C 25.0, H 3.12, N
9.76. Selected IR (Nujol): ν = 1092 (s, νSO dmso-S), 938 (s, νSO
˜
dmso-O), 518 (w, νRu–O), 428 cm–1 (w, νRu–S). 1H NMR
(400 MHz, [D6]acetone, 25 °C): δ = 2.94 (s, 6 H, dmso-O), 3.27 (s,
6 H, dmso-S), 3.35 (s, 6 H, dmso-S), 6.75 (m, 1 H, H4 pz trans to
dmso-O), 6.83 (m, 2 H, H4 pz trans to dmso-S), 8.22 (m, 1 H, H5
pz trans to dmso-O), 8.69 (m, 2 H, H5 pz trans to dmso-S), 8.75
(m, 3 H, H3), 10.19 (s, 1 H, CH) ppm. 1H NMR (400 MHz,
CD3NO2, 25 °C): δ = 2.83 (s, 6 H, dmso-O), 3.17 (s, 6 H, dmso-S),
3.22 (s, 6 H, dmso-S), 6.68 (m, 1 H, H4 pz trans to dmso-O), 6.75
(m, 2 H, H4 pz trans to dmso-S), 8.09 (m, 1 H, H5 pz trans to
dmso-O), 8.46 (m, 2 H, H5 pz trans to dmso-S), 8.62 (m, 3 H, H3),
9.61 (s, 1 H, CH) ppm. 1H NMR (400 MHz, D2O, 25 °C): δ = 2.72
(s, 6 H, free dmso), 3.20 (s, 6 H, dmso-S), 3.29 (s, 6 H, dmso-S),
6.71 (m, 1 H, H4 pz trans to dmso-O), 6.75 (m, 2 H, H4 pz trans
to dmso-S), 8.03 (m, 1 H, H5 pz trans to dmso-O), 8.42 (m, 2 H,
H5 pz trans to dmso-S), 8.53 (m, 3 H, H3), 9.84 (s, 1 H, CH) ppm.
Route b: fac-[Ru(dmso-S)3(dmso-O)3][OTf]2 (0.10 g, 0.11 mmol)
was dissolved in MeOH (5 mL); CH(pz)3 (25 mg, 0.11 mmol) was
added and the mixture was heated to reflux for 30 min. During
reflux the initially colorless solution turned yellow; it was then con-
centrated in vacuo to ca. 1.5 mL and stored at room temperature
after dropwise addition of diethyl ether until saturation. A pale-
yellow microcrystalline precipitate formed within a few days and
was removed by filtration, washed with diethyl ether, and vacuum
dried. Yield: 32 mg (35%). C18H28N6F6O9RuS5 (847.82): calcd. C
25.5, H 3.33, N 9.91; found C 26.0, H 3.23, N 10.06. Crystals suit-
able for X-ray diffraction were obtained by diffusion of diethyl
ether into an acetone solution of 7 (15 mg in 2 mL).
1
microscope and were found to be 13 (by X-ray diffraction and H
NMR spectroscopy). C20H25N3F6O6RuS5 (778.80): calcd. C 30.8,
H 3.23, N 5.39; found C 31.0, H 3.17, N 5.41. 1H NMR (400 MHz,
D2O, 25 °C): δ = 2.52 (s, 3 H, CH3CN), 2.80 (m, 8 H, [9]aneS3),
3.05 and 2.85 (m, 2 H each, [9]aneS3), 7.45 (m, 4 H, mH py), 7.98
(t, 2 H, pH py), 8.61 (d, 4 H, oH py) ppm.
Recrystallization of the remaining mixture from ethanol by dif-
fusion of diethyl ether afforded yellow crystals of pure 11.
C23H27N3F6O6RuS5 (816.85): calcd. C 33.8, H 3.33, N 5.14; found
C 33.9, H 3.27, N 5.27. 1H NMR (400 MHz, D2O, 25 °C): δ = 2.80
(s, 12 H, [9]aneS3), 7.44 (m, 6 H, mH py), 7.98 (t, 3 H, pH py),
8.48 (d, 6 H, oH py) ppm.
As an alternative, fac-[Ru([9]aneS3)(py)3][OTf]2 (11) was selectively
prepared as follows: fac-[Ru([9]aneS3)(dmso)3][OTf]2 (3; 0.1 g,
0.12 mmol) was dissolved in MeOH (5 mL); pyridine (41 μL,
0.5 mmol) was added and the mixture was heated to reflux for 2 h.
The resulting yellow-green solution was concentrated in vacuo to
ca. 2 mL and stored at room temperature after dropwise addition
of diethyl ether until saturation. A yellow crystalline precipitate
formed within 24 h and was then removed by filtration, washed
with chloroform and diethyl ether, and vacuum dried. Yield: 68 mg
(70%). C23H27N3F6O6RuS5 (816.85): calcd. C 33.8, H 3.33, N 5.14;
found C 34.3, H 3.41, N 5.22. 1H NMR (400 MHz, CD3NO2,
25 °C): δ = 2.89 (m, 12 H, [9]aneS3), 7.52 (m, 6 H, mH py), 8.04
(t, 3 H, pH py), 8.50 (d, 6 H, oH py) ppm. ES-MS: m/z (calcd.) =
[(triphos)Ru(μ-Cl)3Ru(triphos)]Cl (8): cis-[RuCl2(dmso)4] (0.48 g,
1 mmol) was dissolved in CHCl3 (20 mL); triphos (0.62 g, 1 mmol)
was added and the mixture was heated to reflux for 4 h under a
stream of Ar. A yellow precipitate formed from the hot orange
solution. After cooling the mixture to room temperature, this pre-
cipitate was removed by filtration, washed with diethyl ether, and
vacuum dried. Yield: 0.6 g (75%). C82H78Cl4P6Ru2 (1593.29):
667.8 ( 667.8) [M – OTf]+, 259.4 (259.2) [M – 2OTf]2+
.
X-ray Crystallography: All diffraction data, with the exception of
3b [150(2) K] were collected at room temperature on a Nonius DIP-
1030H system with graphite-monochromated Mo-Kα radiation. For
each crystal, a total of 30 frames were collected (exposure time of
15–30 min, rotation angle of 6° about φ, with the detector at a
distance of 80–90 mm from the crystal). Cell refinement, indexing,
and scaling of the data sets were done using the programs Mosflm
and Scala.[32] All the structures were solved by Patterson and Fou-
rier analyses and refined by the full-matrix least-squares method
based on F2 with all observed reflections.[33] The choice of the non-
centrosymmetric space group Pna21 for 7 was confirmed by the
successful final refinement; the Flack parameter of 0.49(10) indi-
cates racemic twinning of the crystal. A difference Fourier map of
6 revealed a molecule of dmso and one of water. A residual in 3b
was assigned to a water oxygen (occupancy = 0.5, H atoms omit-
ted). All the calculations were performed using the WinGX System,
Ver. 1.64.05.[34]
1
calcd. C 61.8, H 4.93; found C 60.5, H 4.90. H NMR (400 MHz,
CDCl3, 25 °C): δ = 1.59 (br. s, 6 H, CH3), 2.40 (br. s, 12 H, CH2),
6.83 (m, 24 H, m-Ph), 7.18 (t, 12 H, p-Ph), 7.37 (t, 24 H, o-Ph)
ppm.
fac-[Ru(triphos)(dmso-O)2(H2O)][OTf]2 (9): [(triphos)Ru(μ-Cl)3Ru-
(triphos)]Cl (8; 0.20 g, 0.12 mmol) was dissolved in MeOH
(10 mL); dmso (60 μL, 0.84 mmol) and AgOTf (0.13 g, 0.52 mmol)
were added and the light-protected mixture was heated to reflux
for 2 h. AgCl was removed by filtration and thoroughly washed
with MeOH. The pale-orange solution was concentrated in vacuo
to ca. 2 mL and stored at room temperature after dropwise ad-
dition of diethyl ether until saturation. A pale-yellow microcrystal-
line precipitate formed within 24 h and was removed by filtration,
washed with diethyl ether, and vacuum dried. Yield: 0.2 g (70%).
C47H53F6O9P3RuS4 (1198.1): calcd. C 47.1, H 4.46; found C 46.4,
Crystallographic Data for 2: C11H24ClF3O5RuS6, M = 622.18, tri-
1
¯
H 4.56. H NMR (400 MHz, CDCl3, 25 °C): δ = 1.63 (br. s, 3 H, clinic, space group P1, a = 8.031(3), b = 9.501(3), c = 14.890(4) Å,
CH3), 2.40 (br. s, 6 H, CH2), 2.61 (s, 12 H, free dmso), 7.13 (m, 12 α = 94.48(2)°, β = 104.01(3)°, γ = 89.12(2)°, V = 1099.0(6) Å3, Z =
1028
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 1019–1031

RuII-dmso Precursors with Face-Capping Ligands
FULL PAPER
2, Dc = 1.880 gcm–3, μ(Mo-Kα) = 1.450 mm–1, F000 = 628, θ range
= 2.65–29.01°. Final R1 = 0.0424, wR2 = 0.1130, S = 1.059 for 248
parameters and 8340 reflections, 5152 unique [R(int) = 0.0463], of
which 4233 with I Ͼ 2σ(I); max positive and negative peaks in ΔF
map 0.678, –0.590 eÅ–3.
CCDC-238841 (for 13), -238842 ... -238847 (for 2–8) and -238848
(for 9) contain the supplementary crystallographic data forthis pa-
per. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_requ-
est/cif.
Crystallographic Data for 3b·0.5H2O: C14H31F6O9.50RuS8, M =
822.94, triclinic, space group P1, a = 11.795(3), b = 12.115(3),c
Supporting Information: The molecular structures of trans,cis,cis-
[RuCl2(dmso-S)2(pzH)2] (5) and the cations of fac-[Ru([9]ane-
S3)(py)3][OTf]2·CH3OH (11), fac-[Ru([9]aneS3)(py)2(CH3CN)]-
[OTf]2 (13), and of one of the two crystallographically independent
cations of fac-[Ru([9]aneS3O)(dmso-O)2(dmso-S)][OTf]2 are re-
ported. Of these, only the data for compounds 5 and 13 have been
deposited, as the other structures are of poor resolution mainly
because of the disordered triflate anions. The preparation of fac-
[Ru([9]aneS3O)(dmso-O)2(dmso-S)][OTf]2 is also reported (see also
footnote on the first page of this article).
¯
= 12.878(4) Å, α = 64.96(2)°, β = 66.88(3)°, γ = 71.14(2)°, V =
1505.8(7) Å3, Z = 2, Dc = 1.815 gcm–3, μ(Mo-Kα) = 1.155 mm–1,
F000 = 834, θ range = 1.83–27.48°. Final R1 = 0.0475, wR2 =
0.1234, S = 1.032 for 384 parameters and 10 769 reflections, 6407
unique [R(int) = 0.0626], of which 5004 with I Ͼ 2σ(I); max posi-
tive and negative peaks in ΔF map 0.621, –1.267 eÅ–3.
Crystallographic Data for 4: C14H22Cl2N6O2RuS2, M = 542.47, or-
thorhombic, space group Pbca, a = 16.158(3), b = 13.456(3), c =
21.605(4) Å, V = 4697.4(16) Å3, Z = 8, Dc = 1.534 gcm–3, μ(Mo-
Kα) = 1.093 mm–1, F000 = 2192, θ range = 2.52–28.28°. Final R1 =
0.0494, wR2 = 0.1495, S = 1.079 for 249 parameters and 11 332
reflections, 5780 unique [R(int) = 0.0331], of which 4413 with I Ͼ
2σ(I); max positive and negative peaks in ΔF map 1.164,–
0.474 eÅ–3.
Acknowledgments
Acknowledgments are made for financial support to the donors of
The Petroleum Research Fund, administered by the ACS, (grant
ACS PRF# 38892-AC3), to MIUR (PRIN no. 2003035553), and
to Regione Autonoma Friuli-Venezia Giulia (L. R. 3/98). We wish
to thank Engelhard Italiana S.p.A. for a generous loan of hydrated
RuCl3.
Crystallographic Data for 5: C10H20Cl2N4O2RuS2, M = 464.41, mo-
noclinic, space group P21/n, a = 8.807(3), b = 16.668(4), c =
12.416(4) Å, β = 104.97(2)°, V = 1760.8(9) Å3, Z = 4, Dc
=
1.752 gcm–3, μ(Mo-Kα) = 1.438 mm–1, F000 = 936, θ range = 2.09–
29.92°. Final R1 = 0.0363, wR2 = 0.0925, S = 1.055 for 194 param-
eters and 8455 reflections, 4950 unique [R(int) = 0.0335], of which
4326 with I Ͼ 2σ(I); max positive and negative peaks in ΔF map
0.951, –0.604 eÅ–3.
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Crystallographic Data for 6·dmso·H2O: C14H24Cl2N6O3RuS2, M =
560.48, orthorhombic, space group Pna21, a = 18.614(4), b =
13.631(4), c = 8.585(3) Å, V = 2178.3(11) Å3, Z = 4, Dc
=
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1.709 gcm–3, μ(Mo-Kα) = 1.185 mm–1, F000 = 1136, θ range = 2.65–
26.37°. Final R1 = 0.0656, wR2 = 00.1486, S = 1.039 for 258
parameters and 4527 reflections, 4238 unique [R(int) = 0.0749], of
which 2385 with I Ͼ 2σ(I); max positive and negative peaks in ΔF
map 0.733, –0.803 eÅ–3.
Crystallographic Data for 7: C18H28F6N6O9RuS5, M = 847.83, tri-
¯
clinic, space group P1, a = 9.831(3), b = 13.378(4), c = 14.050(4) Å,
α = 72.72(2)°, β = 69.29(3)°, γ = 72.05(3)°, V = 1607.3(8) Å3, Z =
2, Dc = 1.752 gcm–3, μ(Mo-Kα) = 0.901 mm–1, F000 = 856, θ range
= 2.37–26.37°. Final R1 = 0.0571, wR2 = 0.1509, S = 1.027 for 412
parameters and 10 399 reflections, 6148 unique [R(int) = 0.0494],
of which 4620 with I Ͼ 2σ(I); max positive and negative peaks in
ΔF map 0.733, –0.792 eÅ–3.
Crystallographic Data for 9: C47H53F6O9P3RuS4, M = 1198.11, mo-
noclinic, space group P21/n, a = 18.847(4), b = 15.173(4), c =
18.941(5) Å, β = 97.09(2)°, V = 5375(2) Å3, Z = 4, Dc
=
1.481 gcm–3, μ(Mo-Kα) = 0.608 mm–1, F000 = 2456, θ range = 1.73–
27.48°. Final R1 = 0.0623, wR2 = 0.1703, S = 1.056 for 637 param-
eters and 22 951 reflections, 12 105 unique [R(int) = 0.0746], of
which 6332 with I Ͼ 2σ(I); max positive and negative peaks in ΔF
map 0.477, –1.011 eÅ–3.
Crystallographic Data for 13: C20H25F6N3O6RuS5, M = 778.80, tri-
¯
clinic, space group P1, a = 7.563(2), b = 10.777(3), c = 19.310(4) Å,
α = 97.40(2)°, β = 86.63(3)°, γ = 104.66(3)°, V = 1509.4(7) Å3, Z =
2, Dc = 1.714 gcm–3, μ(Mo-Kα) = 0.942 mm–1, F000 = 784, θ range
= 2.34–27.10°. Final R1 = 0.0550, wR2 = 0.1558, S = 1.040 for 371
parameters and 8918 reflections, 5644 unique [R(int) = 0.0431], of
which 4898 with I Ͼ 2σ(I); max positive and negative peaks in ΔF
map 1.446, –0.499 e·Å–3.
Eur. J. Inorg. Chem. 2005, 1019–1031
www.eurjic.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1029

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cyclononane 1-oxide), whose X-ray structure was determined
(see Supporting information). In this complex one of the S
atoms of the face-capping ligand has been oxidized to SO; the
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bonded and two O-bonded dmso ligands (one is trans to the
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II
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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RuII-dmso Precursors with Face-Capping Ligands
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