Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS-)

Article abstract of DOI:10.1039/c2dt31758c

We have recently reported that cationic thiosulfonato ruthenium complexes [(p-cymene)Ru(bipy)(SSO₂Ar)]⁺ (bipy: 2-2′- bipyridine, Ar: phenyl or p-tolyl) react with thiolates (RS^-, R = alkyl or aryl) by cleavage of the S-SO<

Full text of DOI:10.1039/c2dt31758c

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Influence of the diamine on the reactivity of
thiosulfonato ruthenium complexes with
hydrosulfide (HS−)†
Cite this: Dalton Trans., 2013, 42, 2817
Erwan Galardon,*a Hombeline Daguet,a Patrick Deschamps,b Pascal Roussel,c
Alain Tomasb and Isabelle Artauda
We have recently reported that cationic thiosulfonato ruthenium complexes [(p-cymene)Ru(bipy)-
(SSO2Ar)]+ (bipy: 2-2’-bipyridine, Ar: phenyl or p-tolyl) react with thiolates (RS−, R = alkyl or aryl) by clea-
vage of the S–SO2 bond and formation of a new S–S bond. In this work, we report that the outcome of
the reaction is different if the hydrosulfide anion (R = H) is used, the product obtained being the hydro-
gen(sulfido) derivative [(p-cymene)Ru(bipy)(SH)]+. The bipy ligand is crucial in this result, and its replace-
ment by ethylenediamine leads to a different product, the trisulfido-bridged dinuclear complex
[[(p-cymene)Ru(en)(S)]2S]2+. These two new species have been fully characterized, including by X-ray
diffraction studies, and the two different mechanisms leading to their formation are discussed.
Received 1st August 2012,
Accepted 28th November 2012
DOI: 10.1039/c2dt31758c
www.rsc.org/dalton
nature of the chelating diamine is crucial to the outcome of
the reaction, with either a hydrogen(sulfido) complex or a tri-
Introduction
Sulfur-containing ligands play a major role in coordination sulfido-bridged dinuclear species being isolated. While hydro-
chemistry. This rich chemistry relies on several synthetic path- gen(sulfido) species2 are well documented in ruthenium
ways for the formation of the metal–sulfur bond, the most ver- chemistry, with for example the numerous reactions involving
satile for anionic ligands being the reaction between a metal the cyclopentadienyl derivatives,3 cationic polysulfide deriva-
complex and a sulfur-containing molecule in the presence of a tives are scarce in the literature.
base. However, this procedure is limited by the stability of the
sulfur species under basic conditions, and a number of
ligands, like for instance the sulfonato or disulfanido ligands,
are not accessible using this strategy. We have recently
Experimental section
Physical measurements
reported an original route towards these disulfanido com-
1H NMR spectra were recorded at 300 K on a Bruker ARX-250
plexes by nucleophilic attack of thiolates on ruthenium-bound
thiosulfonato ligands.1 In this reaction, the ruthenium(II)
spectrometer or at 500 MHz on a Bruker AVANCE II-500
centre is crucial, as its kinetic inertness drives the reaction
towards the S–SO2 bond rather than towards the metal centre,
resulting in the cleavage of the thiosulfonate and the for-
mation of a new S–S bond. Here, we report the study of this
reaction carried out with the hydrosulfide anion (HS−). The
spectrometer, and the chemical shifts are calibrated on the
residual solvent peak.4 Fluorescence studies were carried out
on a Hitachi F7000 spectrometer. Elemental analyses were
carried out by the microanalysis service at Gif-sur-Yvette
CNRS. 34S (90%) was purchased from Icon Isotopes.
Materials
aLaboratoire de Chimie et Biochimie Pharmacologique et Toxicologique, UMR 8601
Université Paris Descartes, CNRS, PRES Paris cité, 45 rue des Saints Pères, 75270
Paris cedex 06, France. E-mail: erwan.galardon@parisdescartes.fr
bLaboratoire de Cristallographie et RMN Biologiques, UMR 8015 Université Paris
Descartes, CNRS, PRES Paris cité, 4 avenue de l’Observatoire, 75270 Paris cedex 06,
France
Solvents were distilled using standard techniques and treated
under argon prior to use when necessary. Chemicals were pur-
chased from Aldrich or Thermo-Fischer and used as received.
[(p-Cymene)Ru(bipy)Cl]·PF6 and [(p-cymene)Ru(en)Cl]·PF6
were prepared from the corresponding chloro derivatives by
anion exchange with NH4PF6 in methanol.1,5 The isotopically
labeled 34S phenylthiosulfonate was synthesized by the reac-
tion of the sodium salt of phenylsulfinic acid with elemental
sulfur (resp. 34S) in pyridine.6
cUCCS – Unité de Catalyse et Chimie du Solide, UMR 8012 CNRS, École Nationale
Supérieure de Chimie de Lille, BP 90108-59652 Villeneuve d’Ascq cedex, France
†Electronic supplementary information (ESI) available: Fig. S1–S4 as PDF file.
CCDC 824780, 824781 and 824783. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c2dt31758c
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Synthesis and characterization of the thiosulfonato com- 5.6 Hz), 7.18 (m, 8H), 6.93 (t, 8H, JH–H = 7.2 Hz), 6.80 (m, 4H),
plexes 1a–b and 1′a–b. All the complexes were synthesized 6.04 (d, 2H, JH–H = 6.2 Hz), 5.78 (d, 2H, JH–H = 6.2 Hz), 2.62 (st,
following this general procedure:
a mixture of complex 1H, JH–H = 6.8 Hz), 2.23 (s, 3H), 0.94 (d, 6H, JH–H = 6.8 Hz),
[(p-cymene)Ru(diamine)Cl]·PF6 (0.5 mmol) and silver nitrate −2.51 (s, 1H).
(0.5 mmol) was refluxed under an inert atmosphere in 10 mL
[(p-Cymene)Ru(en)(S)]2S·(BPh4)2 (4′·(BPh4)2). 100 mg of
of degassed methanol for 1 h, filtered, and the thiosulfonate complex 1′a·PF6 (0.16 mmol) was dissolved under argon in
salt (0.55 mmol) added. The reaction mixture was stirred for 2.5 mL of dimethylsulfoxide, and sodium hydrosulfide added
an additional 1 h, and the yellow powder filtered and dried (9 mg, 0.16 mmol). After stirring for 10 min, the solution was
under vacuum (1a–b) or the solvent removed and the residue slowly added to cold diethyl ether to give an oily residue,
purified by chromatography (Sephadex LH-20, methanol, 1′a– which was redissolved in 5 mL of methanol and precipitated
b). Complex 1′a was crystallized as its BPh4 salt by slow by addition of 51 mg of sodium tetraphenylborate. After fil-
diffusion of benzene in a saturated dichloromethane solution tration, 38 mg of 4′·(BPh4)2 was obtained as a yellow powder
of complex 1′a, to give yellow crystals suitable for XRD studies.
(38 mg, 36%). Crystals suitable for XRD studies were obtained
[(p-Cymene)Ru(en)(SSO2(p-tolyl))]·BPh4 (1′a·BPh4). Yield: by layering a concentrated solution of 4′·(BPh4)2 in dichloro-
61%. Anal. calc. (found) for C43H49BN2O2RuS2: C, 64.41 methane with benzene. Anal. calc. (found) for C72H84B2-
(64.29); H, 6.16 (6.12); N, 3.49 (3.44). 1H NMR (δ, DMSO-d6): N4Ru2S3·H2O: C, 64.37 (64.49); H, 6.45 (6.59); N, 4.17 (4.15).
7.78 (d, 2H, JH–H = 8.3 Hz), 7.43 (d, 2H, JH–H = 8.3 Hz), 7.18 (m, ESI+-MS (m/z): 1006 and 1007 (100%, 4′). 1H NMR (δ, DMSO-
8H), 6.93 (t, 8H, JH–H = 8.1 Hz), 6.80 (m, 4H), 6.13 (br, 2H), d6): 7.18 (m, 8H), 6.93 (t, 8H, JH–H = 7.2 Hz), 6.80 (m, 4H), 6.07
5.42 (s, 4H), 4.68 (br, 2H), 2.71 (st, 1H, JH–H = 6.8 Hz), 2.47 (m, (br, 2H), 5.58 (d, 2H, JH–H = 6.0 Hz), 5.50 (d, 2H, JH–H = 6.0 Hz),
2H), 2.45 (m, 2H), 2.42 (s, 3H), 2.11 (s, 3H), 1.11 (d, 6H, JH–H
6.8 Hz).
=
3.84 (br, 2H), 2.83 (st, 1H, JH–H = 6.9 Hz), 2.57 (m, 2H), 2.42
(m, 2H), 2.17 (s, 3H), 1.18 (d, 6H, JH–H = 6.9 Hz).
[(p-Cymene)Ru(en)(SSBz)]·PF6 (2′·PF6). 50 mg of complex 1′
a·PF6 (0.08 mmol) were dissolved in 3 mL of methanol, and a
solution of sodium benzyl thiolate (prepared by mixing 10 μL
of benzylthiol and 80 μL of a 1.0 M solution of sodium meth-
oxide in methanol) added. The yellow solution turned orange,
and was then stirred at r.t. for 1 h. The solvent was then
removed, and the crude product dissolved in a minimum
amount of acetone, filtered, and concentrated to give 2′·PF6 as
an orange powder (26 mg, 51%). Anal. calc. (found) for
C19H29F6N2PRuS2: C, 38.31 (38.31); H, 4.91 (4.86); N, 4.70
(4.68). ESI+-MS (m/z): 451 (100%, 2′). 1H NMR (δ, DMSO-d6):
7.34 (m, 5H), 6.30 (br, 2H), 5.51 (d, 2H, JH–H = 5.6 Hz), 5.40 (d,
2H, JH–H = 5.6 Hz), 3.57 (s, 2H), 3.50 (br, 2H), 2.89 (st, 1H, JH–H
= 6.6 Hz), 2.34 (m, 4H), 2.17 (s, 3H), 1.17 (d, 6H, JH–H = 6.6 Hz).
[(p-Cymene)Ru(bipy)(SH)]·BPh4 (3·BPh4). Method A: 50 mg
of complex 1a·PF6 (0.07 mmol) were dissolved in 1 mL of
dimethylsulfoxide, and sodium hydrosulfide added (5 mg,
0.07 mmol). After stirring for 15 min, the solvent was removed,
and the residue dissolved in 2 mL of methanol. A solution of
27 mg (0.08 mmol) of sodium tetraphenylborate in 0.5 mL of
methanol was then added to yield an orange precipitate. After
filtration, it was dissolved in dichloromethane and the solu-
tion was layered with benzene, to give orange crystals of
3·BPh4. Method B: 200 mg of complex [(p-cymene)Ru(bipy)-
Cl]·PF6 (0.35 mmol) and 59 mg (0.35 mmol) of silver nitrate
were dissolved under argon in 15 mL of methanol, and
Single-crystal X-ray diffraction
Crystal data and experimental conditions are listed in Table 1.
Data were collected with a Bruker SMART APEX CCD diffracto-
meter (Mo-Kα radiation graphite-monochromated radiation, λ
= 0.71073 Å) controlled by the APEX2 software package.7 Data
integration and global cell refinement were performed with
the program SAINT.8 Data were corrected for absorption by the
multiscan semiempirical method implemented in SADABS.9
The structure was solved by direct methods using SHELXS
97.10 Refinement, based on F2, was carried out by full matrix
least squares with SHELXL-97 software.11 Non-hydrogen atoms
were refined using anisotropic thermal parameters. The hydro-
gen atoms were placed in their geometrically generated pos-
itions and allowed to ride on their parent atoms with an
isotropic thermal parameter 20% higher than that of the atom
of attachment. For complex 3, the hydrogen atom attached to
S1 was deduced from a difference Fourier map and refined
with an isotropic temperature factor. The drawings of the
molecules were realized with ORTEP III.12
Results and discussion
Synthesis and characterization of the thiosulfonato complexes
1 and 1′
refluxed for 1 h. After filtration, sodium hydrosulfide (20 mg, For our studies, we used complexes (see Scheme 1) based on
0.35 mmol) was added to the orange solution, which became 2-2′-bipyridine (bipy),1 as well as new complexes based on
brown. After stirring for 1 h, a solution of 123 mg of sodium ethylenediamine (en).
tetraphenylborate (0.38 mmol) in 1 mL of methanol was added
We have already reported the crystal structure of
to precipitate 3·BPh4 as an orange solid (146 mg, 56%). Anal. [(p-cymene)Ru(bipy)(SSO2Ph)]+ 1b in our preliminary report. The
calc. (found) for C44H43BN2RuS·0.7H2O: C, 69.87 (69.90); H, crystal structure of 1′a (see Table 1 for crystal data and struc-
5.92 (5.96); N, 3.70 (3.56). ESI+-MS (m/z): 425 (100%, 3). 1H ture refinements), isolated as its BPh4 salt, is displayed in
−
NMR (δ, DMSO-d6): 9.26 (d, 2H, JH–H = 5.5 Hz), 8.66 (d, 2H, Fig. 1. A list of bond distances and angles is given in Table 2.
JH–H = 8.0 Hz), 8.25 (t, 2H, JH–H = 8.1 Hz), 7.72 (t, 2H, JH–H
=
The ruthenium–sulfur bond is slightly longer than in the
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Table 1 Crystal data and refinement details for 1’a·BPh4, 3·BPh4 and 4’·(BPh4)2
1′a·BPh4
3·BPh4
4′·(BPh4)2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C43H49BN2O2RuS2
801.84
100(2)
Triclinic
ˉ
P1
9.0834(4)
11.4504(4)
19.9443(4)
94.078(2)
97.236(2)
105.574(2)
1970.32(12)
2
C50H49BN2RuS
821.86
293(2)
Monoclinic
P21/c
12.8455(18)
15.144(2)
22.259(3)
90.00
95.330(3)
90.00
C72H84B2N4Ru2S3
1325.37
293(2)
Monoclinic
P21/c
11.221(3)
61.115(17)
10.502(3)
90.00
115.227(5)
90.00
γ (°)
Volume (Å3)
Z
4311.4
4
0.447
6515(3)
4
0.605
μ (mm−1
)
0.542
Reflections collected
Ind. reflections
R(int)
Final R indices
R indices (all data)
67 976
13 099
0.057
0.0373
44 712
9951
0.045
0.0517
0.0641
92 977
14 527
0.043
0.0507
0.0547
0.0706
Table 2 Selected bond distances (Å) and angles (°) for complexes 1’a·BPh4,
3·BPh4 and 4’·(BPh4)2
1′a·BPh4
3·BPh4
4′·(BPh4)2
Ru1–S1
Ru1–N1
Ru1–N2
Ru1–C (average)
Ru2–C (average)
Ru2–N3
Ru2–N4
Ru2–S3
2.4129(5)
2.1330(2)
2.1386(2)
2.207
—
—
—
—
—
2.0284(7)
—
—
89.07(5)
83.55(5)
79.31(7)
—
2.3774(1)
2.074(2)
2.084(3)
2.210
2.3952(12)
2.137(3)
2.131(3)
2.266
2.193
Scheme 1 Thiosulfonato complexes used in this study.
—
—
—
—
—
—
—
2.128(4)
2.110(3)
2.334(2)
2.598(7)
2.0608(17)
1.690(7)
2.196(3)
86.54(9)
85.88(10)
79.23(12)
78.22(16)
94.6(2)
S1–S2
S2–S3
N1–Ru1–S1
N2–Ru1–S1
N1–Ru1–N2
N3–Ru2–N4
N3–Ru2–S3
84.66(8)
84.58(9)
76.74(10)
—
—
—
84.53(16)
81.75(18)
95.04(11)
N4–Ru2–S3
—
—
Fig. 1 ORTEP view of complex 1’a·BPh4 showing thermal ellipsoids at 50%
probability, atom labelling and the hydrogen-bond between O1 and N1. Hydro-
gen atoms and the BPh4 anion are omitted for clarity.
Reactivity of complexes 1 and 1′ with thiolates
related13 thiolato or sulfonato derivatives [(p-cymene)Ru(en)-
(SPh)]+ and [(p-cymene)Ru(en)(S(O)iPr)]+ (0.019 and 0.034 Å,
respectively) but within the range of that observed in the
parent bipyridine complex 1b.1 The difference of electronic
properties between the pure σ-donor ethylenediamine and the
π-acceptor 2-2′-bipyridine in 1b, which can compete with the
arene for the ruthenium electronic density, is illustrated by
the slightly longer ruthenium–arene centroid ring distance in
the former than in the latter (Δ = 0.012 Å).
The crystal structure also confirms that the ethylenedi-
amine ligand can act as a hydrogen-bond donor in arene–ruthe-
nium complexes,13,14 with an N1–H1B⋯O1–S1 interaction
indicated by the N1–O1 distance of 2.880 Å, which correlates
with a longer S1–O1 than an S1–O2 bond.
As anticipated, the thiosulfonato complexes 1 or 1′ react with
thiolates,1 to quantitatively yield the corresponding disulfa-
nido derivatives 2 or 2′, as illustrated in Scheme 2.
Reactivity of complexes 1 and 1′ with hydrosulfide
Complexes 1a and 1′a both instantaneously react with one
equivalent of sodium hydrosulfide in DMSO or DMF. However,
the outcome of the reaction is strongly dependent on the
diamine ligand. The product isolated from the reaction with
1a after precipitation with sodium tetraphenylborate shows a
1
strongly shielded signal at −2.51 ppm in H NMR integrating
for one proton (Fig. S1†). It also gives an ion at m/z = 425
(100%) by ESI+-MS, these data being in agreement with its
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Scheme 2 Reaction of complex 1 or 1’ with sodium benzyl thiolate.
Scheme 3 Favored mechanism for the formation of 4’ from 1’b.
Fig. 2 ORTEP view of complex 3·BPh4 showing thermal ellipsoids at 50% prob-
ability and atom labelling. Hydrogen atoms and the BPh4 anion are omitted for
clarity.
Ru2Sx (x = 5, 6) have been reported.17 The structure of 4′ is best
refined with two occupation sites for S3. Bond distances and
angles (Table 2) are fairly conventional, with nevertheless two
intramolecular hydrogen-bonds detected between the ethylene-
diamine ligand nitrogens N1 and N4 and the central sulfur
atom S2 (N1–S2 and N4–S2 distances are 3.394 and 3.299 Å,
respectively and N1–H1A–S2 and N4–H4–S2 angles are 133.50
and 142.44°, respectively).
The striking difference in the reactivity of complexes 1a and
1′a prompted us to further investigate the mechanisms leading
to the two different products 3 and 4′. Although we had never
observed a direct attack of the sulfur-based nucleophiles onto
the ruthenium centre in our previous studies with thiolates,
this mechanism is however the simplest to explain the for-
mation of complex 3 from 1a. To unambiguously discriminate
between this mechanism and other more complex reaction
pathways, we used the 34S isotopically labeled thiosulfonate
PhSO234S− as a ligand (complex 1b). As expected, the mole-
cular ion in the ESI+-MS spectra of 1b displays an additional +2
Da (m/z = 567 (100%)), confirming the incorporation of the
labeled sulfur in the complex. The ESI+-MS spectrum of
complex 3 obtained after the reaction of 34S-labeled 1b with
sodium hydrosulfide is shown in Fig. S3.† It corresponds to a
hydrogen(sulfido) derivative in which the sulfur is a 32S and
not a 34S, indicating a direct substitution of HS− at the metal
centre. This proposition is further supported by the presence
as major species of PhSO234S− (m/z = 175 (100%)) in the ESI−-
MS spectra. Starting from the corresponding isotopically
enriched complex 1′b, the μ-trisulfido dinuclear complex 4′ is
obtained, its mass spectrum (Fig. S4†) indicating the presence
of two 34S. This is in accordance with a mechanism in which
the hydrosulfide reacts on the S–S(O)2 bond (Scheme 3) rather
than at the metal centre. The breaking of this bond would
result in the formation of the hydrogen(disulfanido) complex
5′, which could then either react with the starting complex 1b′
to give the trisulfido compound 4′, or directly yield 4′ and H2S
by disproportionation. Deprotonation of 5′ by the hydrosulfide
anion could account for the faster reaction of the electrophilic
1b′ with 5′, rather than with the anionic HS−.
Fig. 3 ORTEP view of complex 4’·(BPh4)2 showing thermal ellipsoids at 50%
probability and atom labelling. Hydrogen atoms, the co-crystallized benzene
molecule, and the BPh4 anions are omitted for clarity. The two occupation sites
for S3 are displayed.
formulation as the hydrogen(sulfido) complex [(p-cymene)Ru-
(bipy)(SH)]+ (3). This formulation was confirmed by the syn-
thesis of an authentic sample of 3 from [(p-cymene)Ru(bipy)-
(Cl)]+ and NaSH (see the Experimental section), which shows
the same spectroscopic properties, and by its X-ray structure,
displayed in Fig. 2.
The Ru–S bond distance (2.377 Å) compares well with those
already reported for other monomeric hydrogen(sulfido) Ru(II)
complexes3d,15 or [(p-cymene)Ru(bipy)(SSBz)]+.1 It must be
noted that the crude reaction mixture before precipitation with
sodium tetraphenylborate contains
3 as major species
(Fig. S1′†). In contrast, the reaction of the thiosulfonate
complex 1′a with one equivalent of sodium hydrosulfide leads
to a product lacking the typical strongly shifted signal corre-
sponding to the coordination of an SH group in 1H NMR
(Fig. S2†). This new complex, 4′, isolated as its tetraphenyl-
borate salt, shows an ion in the ESI+-MS spectrum at m/z = 1006
(100%), and its elemental analysis is in accordance with the
formation of the trisulfido-bridged dinuclear complex
[[(p-cymene)Ru(en)(S)]2S·(BPh4)]+. This is further confirmed by its
X-ray structure displayed in Fig. 3.
Structures of transition metal complexes with a single μ-tri-
sulfido bridge are scarce in the literature,16 and none involves
a ruthenium centre. Indeed, with ruthenium, only μ-trisulfido
moieties which are part of a cyclic core of general formula
Thus, the nature of the chelating diamine is a determining
factor in the reaction between thiosulfonato ruthenium
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complexes and hydrosulfide, while it shows no importance in
their reaction with thiolates. Extensive studies have been
carried out on complexes [(η6-arene)Ru(diamine)(Z)]n+ ((Z)
being an anionic or neutral ligand) since the discovery of their
anticancer properties,18 the rationalization of these data is not
straightforward, and electronic as well as steric factors of each
of the three building blocks η6-arene, diamine or Z must be
taken into account. Here, we propose that the more electro-
positive and less sterically crowded metal centre in complexes 1
than in complexes 1′ is at the basis of this switch of reactivity.
5 R. E. Morris, R. E. Aird, P. d. S. Murdoch, H. Chen,
J. Cummings, N. D. Hughes, S. Parsons, A. Parkin, G. Boyd,
D. I. Jodrell and P. J. Sadler, J. Med. Chem., 2001, 44,
3616–3621.
6 J. M. Chalker, Y. A. Lin, O. Boutureira and B. G. Davis,
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7 Bruker AXS Inc., Madison, Wisconsin, USA, 2007.
8 Bruker, Bruker AXS Inc, Madison, Wisconsin, USA, 2007.
9 Bruker AXS Inc., Madison, Wisconsin, USA, 2007.
10 G. M. Sheldrick, University of Gottingen, Germany, 1997.
11 G. M. Sheldrick, University of Gottingen, Germany, 1997.
12 L. J. Farrugia, J. Appl. Crystallogr., 1997, 30, 565.
13 H. Petzold, J. Xu and P. J. Sadler, Angew. Chem., Int. Ed.,
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Conclusions
The reaction between the anion HS− and thiosulfonato ruthe- 14 H. M. Chen, J. A. Parkinson, S. Parsons, R. A. Coxall,
nium complexes, although sensitive to the nature of the metal
coordination sphere, offers a new rational access to rare trisul-
fido-bridged dinuclear derivatives.
R. O. Gould and P. J. Sadler, J. Am. Chem. Soc., 2002, 124,
3064–3082.
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Acknowledgements
We would like to thank the “Agence Nationale pour la
Recherche (ANR)” for funding, through the “Programme JCJC”.
16 (a) M. A. El-Hinnawi, A. A. Aruffo, B. D. Santarsiero,
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Notes and references
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