Substitution and redox reactions of mono- and dinuclear ruthenium complexes containing the pyN2H2S22- ligand [pyN2H2S22- = 2,6-bis(2- mercaptophenylaminomethyl)pyridine(2-)]

Article abstract of DOI:10.1016/j.ica.2004.12.004

In quest of ruthenium complexes having [RuN₃S₂] cores, a non-flexible configuration, trans-thiolate donors and exchangeable coligand L, [Ru(L)(pyN₂H₂S₂)] complexes have been synthesized [pyN2H2S22-=2,6-bis(2-mercaptophenylaminomethyl)pyridine(2-)]. Treatment of [RuCl₂(CH₃CN)₄] with pyN2H2S22- gave [Ru(py)(pyN₂H₂S₂)] (1). The pyridine coligand in 1 proved to be labile and could be substituted by either CO or DMSO under normal conditions to give [Ru(CO)(pyN₂H₂S ₂)] (2) and [Ru(DMSO)(pyN₂H₂S₂)] (3), respectively. Alternatively, 2 could be obtained directly from [RuCl ₂(CH₃CN)₄] and pyN2H2S22-in the presence of CO, whereas the reaction in the absence of CO gave the dinuclear [Ru(pyN ₂H₂S₂)]₂ (8). Treatment of either 2 or 3 with NOBF₄ afforded [Ru^III(CO)(pyN₂H ₂S₂)]BF₄ ([4]BF₄) and [Ru(NO)(pyN₂H₂S₂)]BF₄ ([5]BF ₄), respectively. Treatment of [5]BF₄ with either NEt ₄N₃ or N₂H₄ afforded the amide [Ru(NO)(pyN₂HS₂)] (6) and the hydrazine [Ru(N ₂H₄)(pyN₂H₂S₂)] (7), respectively. Treatment of the dinuclear 8 with either one or two equivalents of NOBF₄ afforded the mixed-valence diruthenium (II,III) [Ru ^IIIRu^II(pyN₂H₂S₂) ₂]BF₄ ([9]BF₄) and the diruthenium (III) [Ru^IIIRu^III(pyN₂H₂S ₂)₂](BF₄) ₂ {[10](BF ₄)₂}, respectively. The diruthenium (III) complex [10](BF₄)₂ is diamagnetic, which can be ascribed to spin-spin pairing between the two Ru^III atoms. A preliminary structure determination of [10](BF₄)₂ supports this observation, indicating a single bond between the two Ru^III atoms. Novel diruthenium complex of this type could be synthesized more generally by treatment of [RuCl₃(MeSPh)₃] with pyN2H2S22-. All complexes were characterized by spectroscopic methods and elemental analysis. The cations [9]⁺ and [10]²⁺ were characterized by X-ray structure analysis.

Full text of DOI:10.1016/j.ica.2004.12.004

Inorganica Chimica Acta 358 (2005) 1798–1806
www.elsevier.com/locate/ica
Substitution and redox reactions of mono- and dinuclear ruthenium
2ꢀ
2ꢀ
q
complexes containing the pyN2H2S2 ligand ½pyN2H2S2
¼
2; 6-bisð2-mercaptophenylaminomethylÞpyridineð2ꢀÞꢁ
ꢀ
*
D. Sellmann , S.Y. Shaban , A. Rosler, F.W. Heinemann
¨
Institut fu¨r Anorganische Chemie der Universita¨t Erlangen-Nu¨rnberg, Egerlandstraße 1, D-91058 Erlangen, Germany
Received 14 May 2004; accepted 12 December 2004
Abstract
In quest of ruthenium complexes having [RuN3S2] cores, a non-flexible configuration, trans-thiolate donors and exchangeable
2ꢀ
coligand L, [Ru(L)(pyN2H2S2)] complexes have been synthesized ½pyN2H2S2 ¼ 2; 6-bisð2-mercaptophenylaminomethylÞ
2ꢀ
pyridine ð2ꢀÞꢁ. Treatment of [RuCl2(CH3CN)4] with pyN2H2S2 gave [Ru(py)(pyN2H2S2)] (1). The pyridine coligand in 1 proved
to be labile and could be substituted by either CO or DMSO under normal conditions to give [Ru(CO)(pyN2H2S2)] (2) and
[Ru(DMSO)(pyN2H2S2)] (3), respectively. Alternatively, 2 could be obtained directly from [RuCl2(CH3CN)4] and pyN2H2S22ꢀin
the presence of CO, whereas the reaction in the absence of CO gave the dinuclear [Ru(pyN2H2S2)]2 (8). Treatment of either 2 or
3 with NOBF4 afforded [RuIII(CO)(pyN2H2S2)]BF4 ([4]BF4) and [Ru(NO)(pyN2H2S2)]BF4 ([5]BF4), respectively. Treatment of
[5]BF4 with either NEt4N3 or N2H4 afforded the amide [Ru(NO)(pyN2HS2)] (6) and the hydrazine [Ru(N2H4)(pyN2H2S2)] (7),
respectively. Treatment of the dinuclear 8 with either one or two equivalents of NOBF4 afforded the mixed-valence diruthenium
(II,III) [RuIIIRuII(pyN2H2S2)2]BF4 ([9]BF4) and the diruthenium (III) [RuIIIRuIII(pyN2H2S2)2](BF4) {[10](BF4)2}, respectively.
2
The diruthenium (III) complex [10](BF4)2 is diamagnetic, which can be ascribed to spin–spin pairing between the two RuIII atoms.
A preliminary structure determination of [10](BF4)2 supports this observation, indicating a single bond between the two RuIII
atoms. Novel diruthenium complex of this type could be synthesized more generally by treatment of [RuCl3(MeSPh)3] with
pyN2H2S22ꢀ. All complexes were characterized by spectroscopic methods and elemental analysis. The cations [9]+ and [10]2+ were
characterized by X-ray structure analysis.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Spin–spin pairing; Ru–Ru single bond; Oxidation; Labile coligand
1. Introduction
oxidation state, type and number of the ligand donor
atoms, and the structure of the metal ligand core [1].
In quest of metal complexes that combine both struc-
tural (metal sulfur sites) and functional (reactivity) fea-
tures of nitrogenase centers, our interest focuses on
complexes with multidentate ligands which contain
amine N, thioether S, and thiolate S donors. Important
requirements for the activation of N2 by nitrogenases
are considered to be electron-rich metal centers [2] as
well as a trans-coordination of the thiolate donors [3].
In order to meet these requirements, we have developed
the [Ru(pyN2H2S2)] fragment [4]. This fragment was
Structure–function relationships of transition metal
complexes are primarily determined by the metal
q
Transition metal complexes with sulfur ligands 166. Part 165: D.
Sellmann, K. Hein, F.W. Heinemann, Inorg. Chim. Acta, 2004, in
press.
*
Corresponding author. Tel.: +49 9131 8527782; fax: +49 9131
8527367.
E-mail address: shaban@anorganik.chemie.uni-erlangen.de (S.Y.
Shaban).
ꢀ
Deceased.
0020-1693/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.12.004

D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
1799
found to bind as yet CO, DMSO and PPh3. The result-
ing complexes exhibit the thiolate and the amine donors
to be in trans-position as well as a high electron density
at the ruthenium centers, as evidenced by the m(CO)
frequency of [Ru(CO)(pyN2H2S2)] (1927 cmꢀ1) [4] but
all complexes [Ru(L)(pyN2H2S2)] (L = CO, DMSO,
PPh3) synthesized so far are extremely substitution inert.
For example, the synthesis of [Ru(CO)(pyN2H2S2)]
from [Ru(DMSO)(pyN2H2S2)] requires 120 ꢁC and
140 bar. Herein, we describe our efforts to synthesize
[Ru(L)(pyN2H2S2)] complexes with labile coligand L,
which may be substituted by nitrogenase-relevant small
molecules. The exchange of L proved to be the major
problem. In the course of our investigations, we have
Treatment of [RuCl2(py)4] with pyN2H2S2–H2 in the
presence of two equivalents of LiOMe (for deprotonation
of the thiol S–H functions) afforded
a
red
[Ru(py)(pyN2H2S2)] (1). The pyridine coligand in com-
plex 1 proved to be labile and could be replaced by either
CO or DMSO at room temperature to afford
[Ru(CO)(pyN2H2S2)] (2) and [Ru(DMSO)(pyN2H2S2)]
(3), respectively. Alternatively, complex 2 could be ob-
tained from [RuCl2(py)4] and pyN2H2S2–Li2 in the pres-
ence of an excess of CO at 65 ꢁC. Complex 2 exhibits a
m(CO) frequency at 1927 cmꢀ1 in KBr indicating a high
electron density at the metal center and a strong Ru–CO
bond, and solid 2 is indeed stable at room temperature
over prolonged periods of time. Complex 3 proved also
substitution inert towards CO, N2H4, N2 or NO ligands.
It could not be reacted with CO at room temperature at
pressures ranging from 1 to 100 bar. Only under very
drastic conditions in an autoclave (140 bar CO, 120 ꢁC),
a slow reaction took place to give complex 2 [4].
In attempts to diminish the substitution inertness,
complexes 2 and 3 were treated with NOBF4. On
addition of NOBF4 to a yellow CH2Cl2 suspension of 2
at 0 ꢁC, a brown suspension was obtained, from which a
brown product was isolated and fully characterized as
[Ru(CO)(pyN2H2S2)]BF4 ([4]BF4) in which the
ruthenium (II) was oxidized to ruthenium (III).
Complex [4]BF4 proved as substitution inert as the
precursor 2. For example, treatment of [4]BF4 with
NaBH4 yielded 2 and showed that the ruthenium
oxidation is reversible. In accordance with expectations,
isolated
a
diamagnetic thiolate-bridged dinuclear
[RuIIIRuIII(pyN2H2S2)2](BF4) {[10](BF4)2} exhibiting
spin–spin pairing as well as a single bond between the
two RuIII centers. Few examples of thiolate-bridged
RuIIIRuIII of this type are known, and most of these
are limited to complexes containingꢀeither Cp* [5] or
other bridging ligands (RCO2ꢀ, OH , and dppm/Clꢀ)
[6] in the coordination sphere.
2. Results and discussion
2.1. Synthesis and reactions of the complexes
Scheme 1 summarizes the syntheses and reactions of
[Ru(pyN2H2S2)] complexes.
N
N
H
H
N
N
S
H
N
S
N
N
S
Ru
Ru
S
N
S
Ru
H
S
N
H
NO
N2H4
6
8
7
2
(j)
(k)
(i)
+
+
N
N
N
H
H
N
S
N
S
NH
S-
HN
-S
Ru
Ru
S
N
S
N
H
H
NO
[5]+
CO
[4]+
(d)
(e)
(h)
(f) (g)
(a)
N
N
N
H
H
H
N
(c)
S
(b)
N
N
S
S
Ru
Ru
py
Ru
S
N
S
N
S
N
H
H
H
CO
DMSO
3
1
2
Scheme 1. Syntheses and reactions of [Ru(pyN2H2S2)] complexes: (a) +[RuCl2(py)4]/MeOH/65 ꢁC; (b) +CO/THF/20 ꢁC; (c) +exc. DMSO/20 ꢁC; (d)
+[RuCl2(CH3CN)4]/CO/MeOH/65 ꢁC; (e) +[RuCl2(DMSO)4]/THF/65 ꢁC; (f) +NOBF4/CH2Cl2/20 ꢁC; (g) +NaBH4/MeOH/20 ꢁC; (h) +NOBF4/
CH2Cl2/20 ꢁC; (i) +NEt4N3/MeOH/20 ꢁC; (j) +N2H4/THF/20 ꢁC; (k) +[RuCl2(CH3CN)4]/MeOH/65 ꢁC.

1800
D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
the oxidation of 2 to yield [4]BF4 shifts the m(CO) band to
higher frequency (ꢂ50 cmꢀ1).
is deshielded relative to the ca. d 7.9 ppm shifts of the
other complexes. One possible reason for that could be
the positive charge of the cation [5]+, which facilitates
proton loss from the NH leading to amide formation.
The limited amide formation of [Ru(pyN2H2S2)]
fragments compared to that of [Ru(N2H2S3)] [8] and
[Ru(N3H3S2)] [9] fragments could be a consequence of
the core structures of [Ru (pyN2H2S2)] complexes that
are expected to disfavor the deprotonation of the
aromatic N–H function into amide function, as it
requires a conversion of tetrahedral four-coordinate N
into planar three coordinate or distorted tetrahedral N
atoms [10] and this could further explain why the
protonation of 6 gave [5]BF4 in only one isomer.
The redox interconversion of 2 and [4]BF4 was also
achieved electrochemically. The cyclic voltammogram
of 2 exhibits two simple successive redox processes. No
reduction waves were observed within the solvent limits.
Thus, the redox process observed at E1/2 = +332 mV is
assignable to the RuII/RuIII couple (2/[4]BF4), whereas
the other at E1/2 = +737 mV results from the RuIII/RuIV
couple. The most remarkable feature is the relatively
large separation between the two redox potentials
(ꢂ400 mV), implying that the RuIII complex [4]BF4 is
fairly stable.
When
a
CH2Cl2 suspension of [Ru(DMSO)
(pyN2H2S2)] (3) was treated with an equimolar amount
of NOBF4, a brown [Ru(NO)(pyN2H2S2)]BF4 ([5]BF4)
was produced. It was surprising to observe such reaction
of 3 with NOBF4 under normal conditions. However,
When a brown THF suspension of [5]BF4 was treated
with excess of anhydrous N2H4, gas was evolved and a
red-brown solid was formed, which exhibits a strong
band in its IR (KBr) spectrum at around 2037 cmꢀ1
,
complex [5]BF4 showed
a
m(NO) frequency at
consistent with the formation of a bound azide complex.
However, this product was so insoluble in all common
solvents that it could not be adequately characterized.
An orange solid was formed upon addition of ether to
the filtrate, which was isolated and characterized as
hydrazine complex [Ru(N2H4)(pyN2H2S2)] (7). Complex
7 demonstrates that the [Ru(pyN2H2S2)] fragment can
bind ‘‘hard’’ r coligands. However, 7 proved too labile
to be used as a starting material. All efforts to oxidize
7 or to get a N2 species by the reaction of N2 with 7
remained as yet unsuccessful, instead dinuclear
[{Ru(pyN2H2S2)}2] (8) was formed.
The dinuclear 8 was found not to react with boiling
DMSO, pyridine, or with CO in these solvents. In
attempts to diminish the inertness, the dinuclear 8 was
treated with different oxidizing agents (see Scheme 2).
Treatment of 8 with one equivalent of NOBF4 in
CH2Cl2 afforded the mixed-valence diruthenium (II,III)
[RuIIRuIII(pyN2H2S2)2]BF4 ([9]BF4). While treatment
of 8 with two equivalents of NOBF4 afforded the
diruthenium (III) [RuIIIRuIII(pyN2H2S2)2](BF4)2 ([10]
(BF4)2). The 1H NMR spectroscopy supports the
diamagnetic nature of [10](BF4)2, in which the chemical
shifts are within the normal diamagnetic range
(1–10 pm). The diamagnetic character of [10](BF4)2 can
be ascribed to the spin–spin pairing between the two
RuIII centers. The preliminary structure of [10](BF4)2
1858 cmꢀ1 in KBr and 1870 cmꢀ1 in MeOH and this
made the cation [5]+ a candidate for attempts to convert
the NO into N2 ligand by addition of nitrogen
nucleophiles to the nitrosyl N atom [7]. For this reason,
complex [5]BF4 was treated with NEt4N3 and N2H4.
Addition of an equimolar amount of NEt4N3 to a
brown suspension of [5]BF4 in MeOH yielded gray,
sparingly soluble product whose elemental analysis
and spectroscopic data were compatible with those
for [Ru(NO)(pyN2HS2)] (6) with one amide donor.
The formation of the amide could further be substanti-
ated by protonation of neutral 6 with HBF4 to afford
isomerically pure [5]BF4. The deprotonation is accom-
panied by a shift of the m(N@O) frequency (KBr) from
1858 cmꢀ1 in [5]BF4 to 1801 cmꢀ1 in 6. The N–H
Broensted acidity could further be established by a
H+/D+ exchange reaction. Addition of D2O to a
DMF solution of [5]BF4 spontaneously afforded [Ru
(NO)(pyN2HDS2)] as shown by the following equation:
½RuðNOÞðpyN2H2S2Þꢁþ ¢ ½RuðNOÞðpyN2HS2Þꢁ þ Hþ
ð1Þ
The Broensted acidity was observed only for the
1
nitrosyl complex [5]BF4 as expected from the H NMR
chemical shift of the NH protons (d 10.5 ppm), which
(a)
(b)
[RuIIRuII(pyN2H2S2)2]
[RuIIRuIII(pyN2H2S2)2]+
[RuII(py)(pyN2H2S2)]
[9]+
1
8
(c)
(d)
(e)
(f)
2-
[RuIIIRuIII(pyN2H2S2)2]2+
pyN2H2S2
[10]2+
Scheme 2. Syntheses and reactions of [{Ru(pyN2H2S2)}2]x+ complexes (x = 0, 1.2): (a) +N2H4/THF/65 ꢁC; (b) +NOBF4/CH2Cl2/20 ꢁC; (c)
+2NOBF4/CH2Cl2/20 ꢁC; (d) +2NOBF4 or I2/CH2Cl2/20 ꢁC; (e) +NaBH4/DMSO/20 ꢁC; (f) +[Ru(Cl)3(MeSPh)3]/THF/MeOH/65 ꢁC.

D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
1801
was also confirmed by X-ray structure analysis which
shows Ru(III)–Ru(III) single bond distance (280.6(2)
pm), consistent with reported values for Ru–Ru single
bonds (260–290 pm) [11]. In an alternative way, the cat-
ion [10]2+ could be synthesized more generally by either
2ꢀ
treatment of [Ru(Cl)3(MeSPh)3] with pyN2H2S2
or treatment of 8 with I2. The electrochemistry of
[10](BF4)2 was studied by cyclic voltammetry. Only one
reduction process was observed within the solvent limit
at E1/2 = ꢀ438 mV, which is assignable to the
RuIIIRuIII/RuIIRuIII couple ([10]2+/[9]+). No oxidation
waves were observed within the solvent limits. The most
remarkable feature is the high potential of the
RuIIIRuIII/RuIIRuIII couple as well as the absence of a
further reduction process RuIIRuIII/RuIIRuII couple,
indicating that the RuIIRuIII complex [9]BF4 is fairly
stable.
2.2. Characterization and general properties of the
complexes
Fig. 1. The CH2 region in 1H NMR of: (a) 1 in pyridine-d5(ꢃ = H2O in
pyridine-d5); (b) [10](BF4)2 in DMSO-d6.
Asfaraspossible, allcomplexeshavebeencharacterized
by common spectroscopic methods and by elemental
analysis. All mononuclear complexes 2, 3, [4]BF4,
[5]BF4, 6 and 7 as well as the dinuclear [9]BF4 and
[10](BF4)2 show moderate solubility in DMF and
DMSO, while complex 1 is soluble only in pyridine
and dinuclear 8 was found to be insoluble in all common
solvents. Consequentially, no NMR spectra of 8 could be
recorded and this complex could be only characterized
by its IR and mass spectra and elemental analysis. The
IR spectra in KBr show weak m(N–H) bands in the
range from 3284 to 3140 cmꢀ1, besides the characteristic
bands of the coligands. For example, strong m(CO)
absorption bands at 1927 and 1975 cmꢀ1 characterize
complexes 2 and [4]BF4, respectively. Strong m(NO)
bands at 1858 and 1801 cmꢀ1 characterize the nitrosyl
complexes [5]BF4 and 6, respectively. Characteristic
strong m(B–F) bands are seen for [4]BF4 (1083 cmꢀ1),
[5]BF4 (1064 cmꢀ1), [9]BF4 (1069 cmꢀ1) and [10](BF4)2
(1074 cmꢀ1), respectively.
sistent with C2-symmetry for all mononuclear
complexes and C1-symmetry for [10](BF4)2. For exam-
ple, the chemically equivalent CH2 protons of the free li-
gand become magnetically nonequivalent in all
mononuclear complexes giving rise to two doublets
and the lower field doublet further splits into a doublet
of doublets due to coupling with the adjacent NH pro-
ton. For [10](BF4)2, the methylene protons are appear-
ing as two doublets and two doublets of doublets in
the low field, indicating C1-symmetry (Fig. 1).
2.3. X-Ray structure determination of [{Ru(pyN2H2S2)}2]
Cl Æ 4MeOH ([9]Cl Æ 4MeOH) and [{Ru(pyN2H2S2)}2]
(BF4)2 Æ 2DMSO Æ acetone Æ n-hexane ([10](BF4)2 Æ 2D-
MSO Æ acetone Æ n-hexane)
The structure of [Ru(pyN2H2S2)]2Cl Æ 4MeOH
([9]Cl Æ 4MeOH) and
a
preliminary structure of
[{Ru(pyN2H2S2)}2](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane
([10](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane) were deter-
mined by X-ray crystallography. [10](BF4)2 proved to
be very difficult to obtain suitable single crystals. A
number of structure determinations attempted so far
resulted always in high residual electron density maxima
close to the two central ruthenium atoms and showed
the presence of numerous solvent molecules. However,
the overall connectivity and geometry of [10](BF4)2
could be established (Fig. 3).
The FD mass spectra exhibit either peaks for the
molecular ions or ions resulting from loss of the coli-
gands. The 13C{1H} NMR spectra proved the most suit-
able spectroscopic probe for determining the symmetry
of the complexes. Nine plus one 13C NMR signals for
the aromatic and the methylene C atoms of the chelate
ligands clearly indicate C2-symmetry for all mononu-
clear complexes.
1
The H NMR spectrum of [10](BF4)2 supports the
Selected bond distances and angles are listed in Table
1. Complexes [9]Cl and [10](BF4)2 contain two C2-sym-
metrical [Ru(pyN2H2S2)] units which are coupled
through thiolate bridges. Each Ru atom is pseudo-octa-
hedrally coordinated by three S and three N donor
atoms. The two thiolate as well as the two amine donors
diamagnetic nature of structure [10](BF4)2, indicating
spin–spin pairing between the two RuIII centers. The
chemical shifts are within the normal diamagnetic range
(0–10 ppm). Seventeen and two 13C NMR signals for the
aromatic and the methylene C atoms for [10](BF4)2 indi-
1
cate C1-symmetry. The H NMR spectra, too, are con-

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D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
N3
N5
N2
Ru1
S1
S4
N2
S2
Ru1
N1
N3
Ru2
S2A
N6
N1A
S1
S5
Ru1A
N4
S1A
N3A
N2A
Fig. 3. The overall connectivity and geometry of the cation
[10]2+ Æ 2DMSO Æ acetone Æ n-hexane, as obtained from a preliminary
X-ray structure determination.
Fig. 2. Molecular structure of the cation of [{Ru(pyN2H2S2)}2]Cl Æ 4-
MeOH ([9]Cl Æ 4MeOH) (50% probability ellipsoids, C-bound
atoms, anions and solvents omitted).
H
This certainly reflects the stability of this dinuclear
complex towards dissociation into [Ru(pyN2H2S2)]
monomers both in solution and in solid state (see Fig. 2).
of the pyN2H2S2 ligand occupy pairwise trans-positions,
thus proving the steric rigidity of the py(CH2)2 back-
bone. The monocation [{Ru(pyN2H2S2)}2]+ contains
two homochiral centers which are rotated against each
other by 84.2ꢁ and the dimeric complex thus possesses
C1-symmetry. Distances and angles show no anomalies.
The Ruꢄ ꢄ ꢄRu distance of [9]Cl Æ 4MeOH [324.6(1) pm]
does not indicate a Ru–Ru bonding interaction, while
the Ruꢄ ꢄ ꢄRu distance of [10](BF4)2 Æ 2DMSO Æ ace-
tone Æ n-hexane [280.6(2) pm] is in the range of the
reported Ru–Ru single bonds (260–290 pm) [11]. The
Ru–NH distances in [9]Cl Æ 4MeOH (mean value ꢂ 216.3
(7) pm) are distinctly longer than the Ru–N (pyridine)
distance (ꢂ202.0 (7) pm). It is also noted that the
Ru1–S5 and Ru2–S2 distances (mean value 237.4 (2)
pm) in the Ru–S(thiolate)–Ru bridges are of the same
length as the Ru–S(thiolate) distances (mean value
236.3 (3) pm) within the two [Ru(pyN2H2S2)] halves.
3. Conclusion
The results reported herein demonstrate that the
2ꢀ
pyN2H2S2 ligand forms ruthenium complexes possess-
ing [Ru(pyN2H2S2)] cores that exhibit the desired con-
figuration with thiolate donors in trans-position and that
are structurally robust. The pyridine coligand in
[Ru(py)(pyN2H2S2)] (1) was found to be labile and
complex 1 can serve as a precursor for other complexes
[Ru(L)(pyN2H2S2)] [L = CO (2), DMSO (3)]. The CO
coligand in 2 was found to be substitution inert and
could not be replaced by NO+, instead oxidation
occurred to give [4]BF4. The DMSO coligand in 3 could
be replaced by NO+ to give [5]BF4. Complex [5]BF4
showed reversible deprotonation of one amine NH
function to give an amide donor ligand. The reaction
of the nitrosyl complex [5]BF4 with N2H4 gave the
hydrazine complex 7, indicating that the [Ru(pyN2H2S2)]
fragment can bind ‘‘hard’’ r coligands.
In the course of our investigations, a series of thiolate-
bridged diruthenium complexes [RuIIRuII(pyN2H2S2)2]
(8), mixed-valence diruthenium (II,III) [RuIIRuIII
(pyN2H2S2)2]BF4 ([9]BF4) and diruthenium (III)
[RuIIIRuIII(pyN2H2S2)2](BF4) {[10](BF4)2} have been
isolated and completely characterized. The diruthenium
(III) [10](BF4)2 is diamagnetic and the diamagnetic
nature is assignable to a spin–spin pairing as well as a
single bond between the two RuIII centers. Few examples
of thiolate-bridged RuIIIRuIII dimers possessing a spin–
spin pairing as well as a single bond between the two
RuIII atoms exist, and these are limited to complexes
containing Cp* in the coordination sphere [5]. RuIIIRuIII
dimers of this type containing other bridging ligands
Table 1
Selected bond distances and angles of [{Ru(pyN2H2S2)}2]Cl Æ 4MeOH
([9]Cl Æ 4MeOH) and [{Ru(pyN2H2S2)}2](BF4)2 Æ 2DMSO Æ acetone Æ n-
hexane ([10](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane)
Complex
[9]Cl Æ 4MeOH
[10](BF4)2 Æ 2DMSO Æ
acetone Æ n-hexanea
Ru1–N1
Ru1–N2
217.8 (6)
217.8 (6)
202.0 (7)
234.7 (3)
237.2 (2)
237.5 (2)
324.6 (1)
85.2 (2)
90.5 (2)
84.2 (2)
78.8 (2)
88.3 (2)
177.6 (2)
216.2 (8)
216.9 (8)
204.8 (8)
240.2 (3)
229.7 (3)
231.4 (3)
280.6 (2)
83.7 (2)
95.2 (3)
84.9 (3)
79.0 (3)
81.8 (3)
166.2 (3)
Ru1–N3
Ru1–S1
Ru1–S2
Ru1–S5/S2A
Ru1–Ru1A/Ru2
N1–Ru1–S1
N2–Ru1–S1
N2–Ru1–S2
N3–Ru1–N1
N3–Ru1–S1
N3–Ru1–S5/S2A
a
Preliminary data.

D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
1803
(RCO2ꢀ, OHꢀ, and dppm/Clꢀ) have been reported [6],
but only very few examples of a thiolato-bridged
RuIIIRuIII dimeric complex that does not contain Cp*
in the coordination sphere are known [5]. The first
example of this type that does not contain Cp* in the
coordination sphere has been reported by Cameron
et al. [11]. Recently, an intermediate complex in the
catalytic transformation of organic disulfides,
[Cp*RuCl(l-SPh)]2, which also has a RuIII–RuIII single
bond, has been isolated [12].
7.02–6.25 (m, 10H, C6H4 + Hb, pyridine), 5.15–5.05 (m,
2H, CHH), 4.62–450 (d, 2H, CHH2). 13C{1H} NMR
([D5]pyridine, 100.4 MHz): d = 159.9, 159.3, 155.3,
150.3, 149.5, 135.9, 132.7, 129.0, 126.9, 132.9, 120.5,
118.3 [C(aryl)], 69.4 (CH2). IR (KBr): m(tilde) = 3244
(w, N–H) cmꢀ1
.
MS (FD+, pyridine): m/z = 452
[Ru(pyN2H2S2)]+. Calc. for C24.5H24N4O0.5RuS2
(547.69): C, 53.73; H, 4.42; N, 10.22. Found: C, 53.41;
H, 4.14; N, 10.05%.
4.2.2. [Ru(CO)(pyN2H2S2)] (2)
(a) From 1: CO gas was bubbled through a red
suspension of 1 (100 mg, 0.19 mmol) in THF (25 ml)
for 5 h in the course of which a yellow solid was
precipitated, which was separated, washed with THF
(20 ml) and CH2Cl2 (20 ml) and dried in vacuo. Yield:
80 mg of [Ru(CO)(pyN2H2S2)] Æ 0.2CH2Cl2 (85%). Calc.
for C20.2H17.4Cl0.4N3ORuS2 (497.57): C, 48.68; H, 3.68;
N, 8.43; S, 12.87. Found: C, 48.78; H, 3.65; N, 8.44%.
(b) From pyN2H2S2-H2: At ꢀ78 ꢁC, n-BuLi (0.34 ml,
0.85 mmol of 2.5 M solution in n-hexane) was added to a
solution of pyN2H2S2–H2 (150 mg, 0.42 mmol) in THF
(60 ml). After warming to room temperature, the
4. Experimental
4.1. General
Unless noted otherwise, all procedures were carried
out under an atmosphere of N2 using Schlenk
techniques. Solvents were dried and distilled before use.
As far as possible, reactions were monitored by IR or
NMR spectroscopy. Spectra were recorded on the
following instruments: IR (KBr discs or CaF2 cuvettes,
solvent bands were compensated): Perkin–Elmer 983,
1620 FT IR, and 16PC FT-IR; NMR: Jeol-JNM-GX
270, EX 270, and Lambda LA 400 with the protio-
solvent signal used as an internal reference. Spectra were
recorded at 25 ꢁC; Mass spectra: Jeol MSTATION 700
spectrometers; Elemental analyses: Carlo Erba EA
1106 or 1108 analyzer; Cyclic voltammetry was
performed with a Radiometer Copenhagen IMT 102
electrochemical interface using a three electrode cell with
a glassy carbon (Radiometer Copenhagen EDI) working
electrode and Pt reference and counter electrodes.
Solutions were 10ꢀ3 M; NBu4[PF6] (10ꢀ1 M) was used
as the supporting electrolyte. Potentials were referenced
to the normal hydrogen electrode (NHE) using Fc/Fc+
as an internal standard E(Fc/Fc+) = +400 mV versus
NHE [13]. [RuCl2(CH3CN)4] [14], [RuCl2(py)4] [15],
[Ru(Cl)3(MeSPh)3] [16] and pyN2H2S2–H2 [4] were
prepared as described in the literature. Anhydrous
hydrazine was obtained by twofold distillation of
hydrazine hydrate over KOH under reduced pressure.
LiOMe was purchased from Aldrich.
solution was combined with
a
solution of
[Ru(Cl)2(CH3CN)4] (143 mg, 0.42 mmol) in MeOH
(30 ml) and heated at 65 ꢁC under bubbling CO for 5 h.
The resultant yellow solid was separated, washed with
MeOH, THF, CH2Cl2 and Et2O (each 10 ml) and dried
in vacuo. Yield: 180 mg of [Ru(CO)(pyN2H2S2)] Æ
1
0.2CH2Cl2 (86%). H NMR ([D6]DMSO, 269.73 MHz):
d = 8.37 (d, 2H, 2NH ), 7.75 (t, JHH = 7.7 Hz, 1H, Hc,
pyridine), 7.40 (d, JHH = 7.9 Hz, 2H, Hb, pyridine),
7.14–7.11 (m, 4H, C6H4), 6.80–6.78 (m, 4H, C6H4),
4.84 (dd, 2H, CHH), 4.48 (d, 2H, CHH). 13C{1H}
NMR ([D6]DMSO, 100.4 MHz): d = 207.2 (C@O),
155.5, 149.9, 149.1, 137.3, 129.9, 126.1, 125.0, 120.5,
120.2 (C[aryl]), 69.2 (CH2). IR (KBr): m(tilde) = 3284
(w, N–H), 1927 (vs, C@O) cmꢀ1. MS (FD, DMSO):
m/z = 481
C
[Ru(CO)(pyN2H2S2)]+.
Calc.
20.2H17.4Cl0.4N3ORuS2 (497.57): C, 48.68; H, 3.68; N,
for
8.43; S, 12.87. Found: C, 48.81; H, 3.20; N; 8.75; S,
12.80%.
4.2.3. [Ru(DMSO)(pyN2H2S2)] (3)
4.2. Syntheses
A red solution of 1 (64 mg, 0.12 mmol) in DMSO
(10 ml) was stirred for 48 h. The resulting yellow
solution was concentrated to 5 ml and combined with
THF (20 ml). The resulting yellow solid was isolated,
washed with THF (20 ml), Et2O (40 ml) and dried in
vacuo. Yield: 54 mg of [Ru(DMSO)(pyN2H2S2)] Æ
DMSO (56%). 1H NMR ([D6]DMSO, 269.73 MHz):
d = 7.47 (m, 3H, Hc, pyridine + 2NH), 7.26–7.18 (m,
6H, Ar–H ), 6.74–6.68 (m, 4H, Ar–H ), 4.65(dd, 2H,
CHH), 4.28 (d, 2H, CHH ), 3.15 (s, 3H, CH3S(O)CH3),
2.75 (s, 3H, CH3S(O)CH3). 13C{1H} NMR ([D6]DMSO,
100.4 MHz): d = 156.78, 150.54, 149.99, 134.3, 130.0,
4.2.1. [Ru(py)(pyN2H2S2)] (1)
A suspension of [Ru(Cl)2(py)4] (306 mg, 0.63 mmol)
and pyN2H2S2–Li2 (230 mg, 0.63 mmol) in MeOH was
heated at 65 ꢁC for 3 h and stirred at 20 ꢁC for 12 h.
The resultant red solid was separated, washed with
MeOH (10 ml) and dried in vacuo. Yield: 340 mg of
[Ru(py)(pyN2H2S2)] Æ 0.5MeOH (98%). 1H NMR
([D5]pyridine, 269.73 MHz): d = 9.23 (d, 2H, 2NH),
8.54 (d, JHH = 5.4 Hz, 2H, Ha, pyridine), 8.00–7.94 (m,
2H, Hc, pyridine), 7.73–7.62 (m, 2H, Hb, pyridine),

1804
D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
125.7, 125.2, 119.7, 119.4 (C[aryl]), 68.7 (CH2), 46.33,
44.20 (DMSO). IR (KBr): m(tilde) = 3110 (w, N–H),
1012 (s, S@O) cmꢀ1. MS (FD, DMSO): m/z = 453
[Ru(pyN2H2S2)]+. Calc. for C23H29N3ORuS4 (592.83):
C, 46.60; H, 4.93; N, 7.09; S, 21.64. Found: C, 46.45;
H, 4.85; N, 7.00; S, 21.60%.
10.62; S, 12.15. Found C, 42.22; H, 3.40; N, 10.55; S,
12.61%.
4.2.7. [Ru(N2H4)(pyN2H2S2)] (7)
A mixture of anhydrous N2H4 (0.5 ml, exc. 1.5 mmol)
and [Ru(NO)(pyN2H2S2)]BF4 (250 mg, 0.44 mmol) in
CH2Cl2 (15 ml) was stirred at 20 ꢁC for 24 h. The
resultant red-brown solid was removed by filtration.
Subsequent addition of Et2O (40 ml) to the filtrate led
to the precipitation of an orange solid, which was
separated, washed with MeOH (10 ml) and Et2O
(20 ml) and dried in vacuo. Yield: 38 mg of
7 Æ 1.8CH2Cl2 Æ CH3CN (14%). 1H NMR ([D6]DMSO,
269.7 MHz): d = 7.54 (m, 3H, 2NH + Hc, pyridine),
7.32–7.26 (m, 5H, Ar–H), 6.78–6.72 (m, 5H, Ar–H),
4.91–4.86 (dd, 2H, CHH), 4.53–4.47 (d, 2H, CHH),
3.23 (s, 2H, NH2), 2.13 (d, 2H, NH2). 13C{1H} NMR
([D6]DMSO, 100.4 MHz): d = 157.44, 151.61, 150.47,
134.28, 130.69, 125.90, 125.27, 119.97, 119.55, (C[Aryl]),
69.1 (CH2). IR (KBr): m(tilde) = 3232, 3141 (w, N–H).
MS (FD+, CH2Cl2): m/z = 452 [Ru(pyN2H2S2)]+, 484
[Ru(N2H4)(pyN2H2S2)]+, 904 [{Ru(pyN2H2S2)}2]+.
Calc. for C22.8H27.6Cl3.6N6RuS2 (679.97): C, 40.25; H,
4.09; N, 12.33. Found: C, 40.16; H, 4.16; N, 12.25%.
4.2.4. [Ru(CO)(pyN2H2S2)]BF4 ([4]BF4)
At 0 ꢁC, solid NOBF4 (10 mg, 0.062 mmol) was
added to a yellow suspension of 2 (30 mg, 0.062 mmol)
in CH2Cl2 (10 ml). The reaction mixture was stirred at
0 ꢁC for 4 h and at 20 ꢁC for 30 min. The resultant
brown solid was collected by filtration, washed with
Et2O (20 ml) and dried in vacuo. Yield: 25 mg of
[Ru(CO)(pyN2H2S2)]BF4 Æ 0.5CH2Cl2 (70.64%). IR
(KBr): m(tilde) = 3240 (w, N–H), 1975 (vs, CO), 1083
(vs, B–F) cmꢀ1. MS (FD, CH2Cl2): m/z = 481 [Ru(CO)
(pyN2H2S2)]+. Calc. for C20.5H18BClF4N3ORuS2
(609.88): C, 40.37; H, 2.97; N, 6.90; S, 10.50. Found:
C, 40.41; H, 2.96; N, 7.20; S, 10.71%.
4.2.5. [Ru(NO)(pyN2H2S2)]BF4 ([5]BF4)
A mixture of NOBF4 (73 mg, 0.62 mmol) and
[Ru(DMSO)(pyN2H2S2)] (330 mg, 0.62 mmol) in
CH2Cl2 (20 ml) was stirred at 20 ꢁC for 48 h. The resul-
tant brown solid was separated by filtration, washed
with CH2Cl2 (20 ml) and n-hexane (20 ml) and dried
in vacuo. Yield: 290 mg of [Ru(NO)(pyN2H2S2)] BF4 Æ
1.5CH2Cl2 Æ 0.75n-hexane (61%). 1H NMR ([D6]DMSO,
269.73 MHz): d = 10.57 (d, 2H, 2NH), 8.00 (t,
JHH = 7.7, 1H, Hc, pyridine), 7.64 (d, JHH = 7.7, 2H,
Hb, pyridine), 7.42 (m, 2H, C6H4), 7.24 (m, 2H,
C6H4), 7.08 (m, 4H, C6H4), 5.33 (dd, 2H, CHH), 4.94
(d, 2H, CHH). 13C{1H} NMR ([D6]DMSO,
100.4 MHz): d = 156.0, 147.9, 147.3, 141.78, 132.1,
129.1, 125.3, 124.1, 122.6 (C[aryl]), 69.5 (CH2). IR
(KBr): m(tilde) = 3218 (w, N–H), 1858 (vs, NO), 1064
(vs, B–F) cmꢀ1. MS (FD, CH2Cl2): m/z = 483 [Ru(NO)
(pyN2H2S2)]+. Calc. for C25H30.5BCl3F4N4ORuS2
(761.41): C, 39.44; H, 4.03; N, 7.36. Found: C, 39.53;
H, 3.76; N, 7.56%.
4.2.8. [{Ru(pyN2H2S2)}2] (8)
A yellow suspension of pyN2H2S2-H2 (284 mg,
0.8 mmol), LiOMe (1.6 ml, 1.6 mmol of 1 N solution
in MeOH) and [Ru(Cl)2(CH3CN)4] (270 mg, 0.8 mmol)
in MeOH (30 ml) was heated at 65 ꢁC for 3 h. The
resulting fine red crystals were separated, washed with
MeOH (20 ml) and Et2O (30 ml) and dried in vacuo.
Yield: 230 mg of 8 Æ MeOH (62%). IR (KBr): m(tilde) =
3252, 3242 (w, N–H). MS (FD+, DMSO): m/z = 904
[{Ru(pyN2H2S2)}2]+. Calc. for C39H38N6Oru2S4
(937.17): C, 49.98; H, 4.09; N, 8.97; S, 13.69. Found:
C, 49.81; H, 3.82; N, 8.94; S, 13.54%.
4.2.9. [Ru(pyN2H2S2)]2BF4 ([9]BF4)
A red mixture of 8 (134 mg, 0.15 mmol) and NOBF4
(17 mg, 0.15 mmol) in CH2Cl2 (25 ml) was stirred at
ꢀ78 ꢁC for 2 h and at 20 ꢁC for 48 h in the course of
which a green solid was precipitated, which was
separated, washed with CH2Cl2 (20 ml) and n-hexane
(10 ml) and dried in vacuo. Yield: 130 mg of
[{Ru(pyN2H2S2)}2]BF4 Æ CH2Cl2 (80%). IR (KBr):
m(tilde) = 3245, 3236 (w, N–H), 1069 (s, B–F). MS
(FD+, DMSO): m/z = 904 [{Ru(pyN2H2S2)}2]+. Calc.
for C39H36N6BCl2F4Ru2S4 (1067.87): C, 43.50; H,
3.37; N, 7.80; S, 11.91. Found: C, 43.45; H, 3.46; N,
7.79; S, 11.93%.
4.2.6. [Ru(NO)(pyN2HS2)] (6)
A mixture of NEt4N3 (0.60 mg, 0.33 mmol) and
[Ru(NO)(pyN2H2S2)]BF4 (185 mg, 0.33 mmol) in
MeOH (20 ml) was stirred at 20 ꢁC for 4 h in the course
of which a gray solid was formed which was collected by
filtration, washed with MeOH, H2O and Et2O (each
20 ml) and dried in vacuo. Yield: 100 mg [Ru(NO)
(pyN2HS2)] Æ 2.5H2O (64%). 1H NMR ([D7]DMF,
269.7 MHz): d = 7.76 (t, 1H, Hc, pyridine), 7.50 (d,
2H, C6H4), 7.19 (d, 4H, C6H4), 6.93 (t, 3H, C6H4),
6.80 (b, 1H, NH), 5.52 (d, 2H, CH H), 5.10 (d, 2H,
CHH). IR (KBr) m(tilde) = 1801 (vs, NO) cmꢀ1. MS
(FD+, CH2Cl2): m/z = 482 [Ru(NO)(pyN2HS2)]+. Calc.
for C19H21N4RuO2.5S2 (536.60): C, 42.53; H, 3.25; N,
4.2.10. [{Ru(pyN2H2S2)}2](BF4)2 ([10](BF4)2)
(a) From 1. A mixture of 1 (100 mg, 0.19 mmol) and
NOBF4 (22 mg, 0.19 mmol) in CH2Cl2 (20 ml) was
heated at 20 ꢁC for 12 h. In the course of which a green

D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
1805
solid was precipitated, which was separated, washed
with CH2Cl2 (20 ml) and n-hexane (10 ml) and dried
in vacuo. Yield: 60 mg of [{Ru(pyN2H2S2)}2] (BF4)2
(68%).
(each 30 ml) was heated at 65 ꢁC for 4 h. The resulting
fine green crystals were separated by filtration, washed
with MeOH (20 ml) and ether (30 ml) and dried in va-
cuo. Yield: 130 mg of [10](Cl)2 Æ MeOH (26%). IR
(KBr): m(tilde) = 3232 (w, N–H). MS (FD+, DMSO):
m/z = 904 [{Ru(pyN2H2S2)}2]+. Calc. for C39H38N6Cl2-
ORu2S4 (1008.08): C, 46.47; H, 3.80; N, 8.34; S, 12.72.
Found: C, 46.39; H, 3.77; N, 8.13; S, 12.62%.
(b) From 8: A red suspension of 8 (156 mg,
0.17 mmol) and NOBF4 (40 mg, 0.34 mmol) in CH2Cl2
(20 ml) was heated at 20 ꢁC for 24 h. The resultant green
solid was separated by filtration, washed with CH2Cl2
(20 ml) and n-hexane (10 ml), dried in vacuo and
recrystallized from CH2Cl2/DMSO/n-hexane (10:1:10)
to give a green solid. Yield: 110 mg of [10](BF4)2
4.2.12. [{Ru(pyN2H2S2)}2](I)2([10](I)2)
A red suspension of 8 (100 mg, 0.11 mmol) and I2
(28 mg, 0.11 mmol) in CH2Cl2 (20 ml) was stirred at
20 ꢁC for 48 h in the course of which a green solid was
precipitated, separated, washed with CH2Cl2 (10 ml)
and n-hexane (10 ml) and dried in vacuo. Yield: 120 mg
of [10](I)2 Æ 0.5CH2Cl2 (91%). IR (KBr): m(tilde) =
3241 (w, N–H). MS (FD+, DMSO): m/z = 904
[{Ru(pyN2H2S2)}2]+. Calc. for C38.5H35N6ClI2Ru2S4
(120141): C, 38.49; H, 2.94; N, 6.70; S, 10.68. Found:
C, 38.48; H, 3.13; N, 6.52; S, 10.48%.
1
(60%). H NMR ([D6]DMSO, 269.7 MHz): d = 7.97 (t,
JHH = 7.9 Hz, 2H, Hc, pyridine), 7.68 (d, 2H, NH),
7.61 (d, JHH = 7.7 Hz, 2H, Hb, pyridine), 7.53 (d,
JHH = 7.7 Hz, 2H, Hb, pyridine), 7.40–5.90 (m, 16H,
C6H4), 4.92 (dd, 2H, CHH), 4.83 (dd, 2H, CHH), 4.70
(d, 2H, CHH), 4.03 (d, H, CHH), 3.83 (d, 2H, NH).
13C{1H} NMR ([D6]DMSO, 100.4 MHz): d = 158.5,
156.3, 146.8, 145.6, 141.1, 140.6, 139.8, 131.2, 130.1,
129.0, 127.5, 127.3, 126.2, 123.6, 123.0, 122.6, 122.0
(C[Aryl]), 70.61, 67.8 (CH2). IR (KBr): m(tilde) = 3234
(w, N–H), 1074 (vs, B–F). MS (FD+, DMSO): m/z =
904 [{Ru(pyN2H2S2)}2]+. Calc. for C38H34N6B2F8Ru2S4
(1078.74): C, 42.31; H, 3.18; N, 7.79. Found: C, 42.11;
H, 3.26; N, 8.12%.
4.3. X-ray structure analysis of [{Ru(pyN2H2S2)}2]Cl Æ
4MeOH ([9]Cl Æ 4MeOH) and preliminary X-ray
structure analysis of [{Ru(pyN2H2S2)}2](BF4)2
Æ
2DMSO Æ acetone Æ n-hexane ([10](BF4)2 Æ 2DMSO Æ
acetone Æ n-hexane)
4.2.11. [{Ru(pyN2H2S2)}2](Cl)2 ([10](Cl)2)
A suspension of pyN2H2S2-H2 (355 mg, 1.0 mmol),
LiOMe (2 ml, 2 mmol of 1 N solution in MeOH) and
[Ru(Cl)3(MeSPh)3] (582 mg, 1.0 mmol) in MeOH/THF
Black block-shaped single crystals of [9]Cl Æ 4MeOH
were grown at room temperature by slow air diffusion
of a solution of [{Ru(pyN2H2S2)}2] (8) into a mixture
Table 2
Selected crystallographic data of [{Ru(pyN2H2S2)}2]Cl Æ 4MeOH ([9]Cl Æ 4MeOH) and [{Ru(pyN2H2S2)}2](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane
([10](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane)
Compound
[9]Cl Æ 4MeOH
[10](BF4)2 Æ 2DMSO Æ acetone Æ n-hexanea
Formula
Mr (g molꢀ1
C42H50ClN6O4Ru2S4
1068.71
0.50 · 0.40 · 0.30
8720
C51H66B2F8N6O3Ru2S4
1379.22
0.40 · 0.38 · 0.30
2816
)
Crystal size (mm)
F(0 0 0)
Crystal system
Space group
a (pm)
orthorhombic
Fdd2
monoclinic
C2/c
3036.2 (9)
3574 (2)
1659.3 (5)
18.11 (1)
16
2121.8 (4)
1861.1 (4)
1502.1 (3)
5.909 (2)
4
b (pm)
c (pm)
V (nmꢀ3
)
Z
qcalc (g cmꢀ3
)
1.577
0.964
298
1.550
0.795
200
l (mmꢀ1
T (K)
)
h Range (ꢁ)
1.76–27.01
5815
5434
2.8–52.0
7106
5814
Measured reflection
Unique reflection
Rint
0.0205
3881
Observed reflection
r Criterion
Reflection parameters
R1/wR2
Absolute structure parameter [19]
3696
F0 > 4.0r(F)
540
F0 > 4.0r(F)
356
0.0894/0.2136
0.0415/0.0880
0.05 (4)
a
Preliminary data.

1806
D. Sellmann et al. / Inorganica Chimica Acta 358 (2005) 1798–1806
(b) K. Burger, in: K. Burger (Ed.), Biocoordination Chemistry,
Ellis Horwood, New York, 1990, p. 11.
of MeOH and CH2Cl2 (1:1) in the course of 48 h. Green
single crystals of poor quality of [10](BF4)2 Æ
2DMSO Æ acetone Æ n-hexane were grown by layering a
solution of [10](BF4)2 in DMSO/acetone (1/3) with
n-hexane at ꢀ20 ꢁC within one week.
[2] (a) R.A. Henderson, G.J. Leigh, C.J. Picket, Adv. Inorg. Chem.
Radiat. 27 (1983) 245;
(b) H. Kandler, C. Gauss, W. Bidell, S. Rosenberger, T. Burgi,
¨
I.L. Eremenko, D. Veghini, O. Orama, P. Burger, H. Berke, J.
Am. Chem. Soc. 110 (1988) 4872;
Single crystals were sealed under N2 in a glass
capillary; data were collected either on a Nicolet
R3m/V ([9]Cl Æ 4MeOH) or a Siemens P4 ([10](BF4)2 Æ
2DMSO Æ acetone Æ n-hexane) diffractometer using Mo
Ka radiation (k = 71.073 pm, graphite monochromator).
For [10](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane, an empirical
absorption correction using XABS2 [17] has been
performed, while for [9]Cl Æ 4MeOH absorption effects
have been neglected. The structures were solved by
direct methods and refined on F2 using full-matrix least
squares procedures (SHELXTL NT 5.10 [18]). Hydrogen
atoms were geometrically positioned and allowed to ride
on their carrier atoms with an isotropic displacement
parameter fixed at 1.2 or 1.5 times Ueq of the proceed-
ing C, N, or O atom. Table 2 lists selected crystallo-
graphic data. X-ray structure determination of
[10](BF4)2 Æ 2DMSO Æ acetone Æ n-hexane suffered from
high residual electron density maxima localized in vicin-
ity of the two Ru centers and probably disordered
solvent molecules.
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8
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5. Supplementary material
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Crystallographic data (excluding structure factors) for
the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as
Supplementary Publication Nos. CCDC 238306 and
238307. Copies of the data can be obtained free of charge
on application to CCDC, 12 Union Road, Cambridge
CB 21 EZ, UK (fax: +44 1223 336 033; e-mail: deposit
@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
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Acknowledgments
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(1960) 483;
We thank Professor Dr. Horst Kisch for his helpful
suggestions. Financial support for this work by the
Deutsche Forschungsgemeinschaft (SFB 583 ꢁRedox-
Active metal complexesꢂ) and Fonds der Chemischen
Industrie is gratefully acknowledged.
(b) G. Gritzner, J. Kuta, Pure Appl. Chem. 56 (1984) 461.
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