Di- and tri-nuclear ruthenium nitrosyl complexes containing thiolate ligands

Article abstract of DOI:10.1016/j.jorganchem.2016.02.004

Treatment of Ru(NO)Cl₃ with NaSC₆F₄H (C₆F₄HSH = 2,3,5,6-tetrafluorothiophenol) afforded the hydroxo-bridged dimer Na(H₂O)₂[Ru(NO)(SC₆HF₄)₂]₂(μ-SC₆HF₄)₂(μ-OH) (Na(H₂O)₂1), in which the {Na(H₂O)₂}⁺ moiety binds to the diruthenium core via the μ-hydroxo ligand and three ortho fluorine atoms of the thiolate ligands. Metathesis of Na(H₂O)₂1 with Buⁿ ₄NBr and Ph₄PCl afforded Na-free (Buⁿ ₄N)[1] and (Ph₄P)[1], respectively. Treatment of Ru(NO)Cl₃ with NaSBu^t afforded the trinuclear oxo-sulfido cluster Na(H₂O)₂[Ru(NO)(SBu^t)(μ-SBu^t)]₃(μ₃-S)(μ₃-O) (Na(H₂O)₂2) that contains a trinuclear {Ru₃(SBu^t)₃} core capped by a μ₃-oxo and a μ₃-sulfido ligand. The {Na(H₂O)₂}⁺ moiety binds to the triruthenium core via the μ₃-oxo and two terminal thiolate ligands. Metathesis of Na(H₂O)₂2 with Buⁿ ₄NBr gave (Buⁿ ₄N)[2]. Treatment of Ru(NO)Cl₃ with NaStipp (tipp = 2,4,6-triisopropylphenyl) gave mononuclear Ru(NO)(Stipp)₃(tippSH) (3). The crystal structures of Na(H₂O)₂1, (Ph₄P)[1], and Na(H₂O)₂2 have been determined.

Full text of DOI:10.1016/j.jorganchem.2016.02.004

Journal of Organometallic Chemistry xxx (2016) 1e7
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Di- and tri-nuclear ruthenium nitrosyl complexes containing thiolate
ligands
Ka-Wang Chan, Wai-Ming Ng, Wai-Man Cheung**, Chun-Sing Lai, Herman H.Y. Sung,
Ian D. Williams, Wa-Hung Leung*
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Treatment of Ru(NO)Cl3 with NaSC6F4H (C6F4HSH ¼ 2,3,5,6-tetrafluorothiophenol) afforded the hydroxo-
bridged dimer Na(H2O)2[Ru(NO)(SC6HF4)2]2(m-SC6HF4)2(m
-OH) (Na(H2O)21), in which the {Na(H2O)2}þ
Received 22 May 2015
Received in revised form
28 January 2016
Accepted 2 February 2016
Available online xxx
moiety binds to the diruthenium core via the m-hydroxo ligand and three ortho fluorine atoms of the
thiolate ligands. Metathesis of Na(H2O)21 with Bun4NBr and Ph4PCl afforded Na-free (Bun4N)[1] and
(Ph4P)[1], respectively. Treatment of Ru(NO)Cl3 with NaSBut afforded the trinuclear oxo-sulfido cluster
Na(H2O)2[Ru(NO)(SBut)( -SBut)]3(m3-S)(m3-O) (Na(H2O)22) that contains a trinuclear {Ru3(SBut)3} core
m
This paper is dedicated to the memory of
Prof. Jack Lewis
capped by a m3-oxo and a m3-sulfido ligand. The {Na(H2O)2}þ moiety binds to the triruthenium core via
the m3-oxo and two terminal thiolate ligands. Metathesis of Na(H2O)22 with Bun4NBr gave (Bun4N)[2].
Treatment of Ru(NO)Cl3 with NaStipp (tipp ¼ 2,4,6-triisopropylphenyl) gave mononuclear Ru(NO)(S-
tipp)3(tippSH) (3). The crystal structures of Na(H2O)21, (Ph4P)[1], and Na(H2O)22 have been determined.
© 2016 Elsevier B.V. All rights reserved.
Keywords:
Ruthenium
Nitrosyl
Thiolate
Cluster
1. Introduction
obtained from the reaction of [Fe(SBut)4]2ꢀ with NO [6].
Ruthenium nitrosyl thiolate complexes have been found to
Transition-metal thiolate complexes have attracted much
attention because they are relevant to the active sites of metal-
loenzymes [1] and heterogeneous catalysts [2]. Of particular in-
terest are ruthenium complexes in sulfur-rich ligand environments
because RuS2 has been shown to be a highly active catalyst for
industrially important hydrodesulfurization processes [3]. Also,
molecular ruthenium-sulfur complexes have been used as catalysts
for organic synthesis [4].
display interesting organometallic chemistry. Previously, Millar,
Koch and co-workers reported that the reaction of the anionic Ru
nitrosyl complex K2[Ru(NO)Cl5] with NaSR (R ¼ substituted phenyl)
afforded [Ru(NO)(SR)4]ꢀ, which lost NO to give Ru(SR)4 that fea-
tures an agostic interaction between Ru and one CeH group (for
R ¼ 2,4,6-triisopropylphenyl) or underwent cyclometalation to
yield
dinuclear
[(Ru(
m
-S-2-CH2-3,5,6-Me3C6H)(S-2,3,5,6-
(for 2,3,5,6-
Me4C6H)(NO))2(
m
-S-2,3,5,6-Me4C6H)]ꢀ
R
¼
Our interest in nitrosyl thiolate complexes is stimulated by a
report that a ruthenium nitrosyl complex containing a chelating
thiolate ligand releases NO readily upon irradiation with visible
light [5]. This finding suggests that ruthenium nitrosyl thiolate
complexes may find applications as photoactive NO release agents.
The formation of group 8 metal thiolate nitrosyl complexes is also
potentially relevant to the mechanism of NO-mediated degradation
of iron-sulfur clusters. For example, [Fe(SBut)3(NO)]ꢀ has been
tetramethylphenyl) [7]. To further explore the organometallic
chemistry of ruthenium nitrosyl thiolate complexes, we sought to
investigate the reaction of charge-neutral Ru(NO)Cl3 with sodium
thiolates. In this work, we found that the outcome of the reaction of
Ru(NO)Cl3 with NaSR is dependent on the steric and electronic
factors of R. For the reaction with 2,3,4,6-tetrafluorothiophenolate,
a dinuclear hydroxo-bridged nitrosyl complex was obtained. On the
other hand, the reaction with tert-butylthiolate led to formation of
a trinuclear oxo-sulfido cluster, presumably via CeS cleavage of the
thiolate. Using sterically bulky 2,4,6-triisopropylthiphenolate, a
mononuclear Ru nitrosyl thiolate complex was isolated. The solid-
state structures of these Ru nitrosyl thiolates have been established
by X-ray crystallography.
* Corresponding author.
** Corresponding author.
E-mail addresses: cheungwm@ust.hk (W.-M. Cheung), chleung@ust.hk
(W.-H. Leung).
http://dx.doi.org/10.1016/j.jorganchem.2016.02.004
0022-328X/© 2016 Elsevier B.V. All rights reserved.
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2
K.-W. Chan et al. / Journal of Organometallic Chemistry xxx (2016) 1e7
2. Experimental section
OH), 7.84e8.03 (m, 20H, phenyl), 7.21e7.35 (m, 6H, phenyl) ppm.
19F NMR (376 MHz, acetone-d6):
¼ ꢀ141.65 (m, 16F), ꢀ131.05 (m,
8F) ppm. 31P {1H} NMR (162 MHz, acetone-d6):
¼ 24.14 (s) ppm. IR
(KBr, cmꢀ1): 1865 [
(NeO)], 3448 [ (OeH)].
d
2.1. General
d
n
n
All manipulations were carried out under nitrogen using stan-
dard Schlenk techniques. Solvents were dried, distilled and
degassed prior to use. NMR spectra were recorded on a Bruker AV
400 MHz spectrometer operating at 400, 162, and 376 MHz for 1H,
2.5. Preparation of Na(H2O)2[Ru(NO)(SBut)( -SBut)]3(m3-S)(m3-O)
m
(Na(H2O)22)
31P, and 19F, respectively. Chemical shifts (
with reference to SiMe4 (1H), H3PO4
d
, ppm) were reported
To a solution of Ru(NO)Cl3 (24 mg, 0.10 mmol) in thf (10 mL) was
added 3 equivalents of NaSBut (34 mg, 0.3 mmol). The reaction
mixture was stirred at room temperature for 12 h. The volatiles
were removed in vacuo, and the residue was extracted with hex-
anes. Recrystallization from hexanes at room temperature afforded
red crystals which were suitable for X-ray analysis. Yield: 36 mg
(
31P) and C6H5CF3 19F).
(
Infrared spectra were recorded on a Perkin-Elmer 16 PC FT-IR
spectrophotometer, and mass spectra on a Finnigan TSQ 7000
spectrometer. Elemental analyses were performed by Medac Ltd.,
Surrey, UK. Ru(NO)Cl3 was prepared by treatment of Ru(NO)
Cl3$xH2O (Strem Ltd) with excess trimethylsilylchloride in CH2Cl2.
The volatiles were then removed in vacuo and the dark residue was
washed with hexanes. 2,4,6-Triisopropylthiophenol was synthe-
sized according to a literature method [8]. Sodium thiolates (NaSR)
were prepared by reaction of RSH with NaH (60% in mineral oil) in
tetrahydrofuran (thf). The volatiles were then removed in vacuo
and the white residue was recrystallized from thf/hexanes. Other
chemicals were purchased from Sigma-Aldrich Ltd and use as
received.
(76%). 1H NMR (400 MHz, acetone-d6):
d
¼ 1.80 (s, 27H, But), 1.91 (s,
27H, But), 3.02 (br. s, 4H, H2O) ppm. IR (KBr, cmꢀ1): 1786 [
n(NeO)],
1792 [n(NeO)], 1801 [n
(NeO)]. MS (FAB): m/z 967 (Mþ e 2H2O e S).
Anal. Calcd for C24H58N3NaO6Ru3S7$H2O: C, 27.36; H, 5.74; N, 3.99;
S, 21.29. Found: C, 27.16; H, 5.44; N, 3.55; S, 21.12.
2.6. Preparation of (Bun4N)[{Ru(NO)(SBut)( -SBut)}3(m3-S)(m3-O)]
m
((Bun4N)[2])
To a solution of Na(H2O)22 (40 mg; 0.040 mmol) in methanol
(2 mL) was added Bun4NBr (52 mg; 0.160 mmol) in water (3 mL).
The red precipitate was washed with water (3 ꢁ 2 mL), and
recrystallized from CH2Cl2/hexanes. Yield: 39 mg (78%). 1H NMR
2.2. Preparation of Na(H2O)2[Ru(NO)(SC6HF4)2]2(m-SC6HF4)2(m-
OH) (Na(H2O)21)
To a solution of Ru(NO)Cl3 (24 mg, 0.10 mmol) in thf (10 mL) was
added 3 equivalents of NaSC6HF4 (61 mg, 0.3 mmol). The mixture
was stirred at room temperature for 12 h and the volatiles were
removed in vacuo. The residue was washed with hexanes and
extracted with Et2O. Recrystallization from Et2O/hexanes at room
temperature afforded red crystals. Yield: 61 mg (85%). 1H NMR
(400 MHz, acetone-d6):
d
¼ 0.18 (t, J ¼ 7.2 Hz, 12H, CH3CH2CH2CH2),
0.60e0.73 (m, 8H, CH3CH2CH2CH2), 1.05e1.13 (m, 8H,
CH3CH2CH2CH2), 1.81 (s, 27H, But), 1.94 (s, 27H, But), 2.58 (t,
J ¼ 7.3 Hz, 8H, CH3CH2CH2CH2) ppm. IR (KBr, cmꢀ1): 1752 [
n(NeO)],
1774 [n(NeO)].
(400 MHz, acetone-d6):
d
¼ 2.30 (br. s, 1H, OH), 2.87 (br. s, 4H, H2O),
2.7. Preparation of Ru(NO)(Stipp)3(tippSH) (tipp ¼ 2,4,6-
triisopropylphenyl) (3)
7.06e7.30 (m, 4H, phenyl), 7.52e7.63 (m, 2H, phenyl) ppm. 19F NMR
(376 MHz, acetone-d6):
d
¼ ꢀ142.1 (m, 8F), ꢀ140.4 (m, 8F), ꢀ132.28
(m, 4F), ꢀ130.45 (m, 4F) ppm. IR (KBr, cmꢀ1): 1887 [
n
(NeO)], 3446
To a solution of Ru(NO)Cl3 (24 mg, 0.10 mmol) in thf (10 mL) was
added 4 equivalents of NaStipp (103 mg, 0.40 mmol). The mixture
was stirred at room temperature for 12 h. The solvent was pumped
off and the residue was extracted with hexanes/CH2Cl2 (10:1, v/v).
Recrystallization from CH2Cl2/hexanes at ꢀ20 ꢂC afforded brown
[n
(OeH)]. MS (FAB): m/z 1387 (Mþ e 2H2O), 1364 (Mþ e 2H2O e
Na), 1221 (Mþ
36H11F24N2NaO5Ru2S6$1.25Et2O: C, 32.44; H, 1.56; N, 1.85. Found:
C, 32.67; H, 1.27; N, 2.04.
e 2H2O e Na e SC6HF2). Anal. Calcd for
C
crystals. Yield: 75 mg (70%). 1H NMR (400 MHz, CDCl3):
d
¼ 1.25 (m,
2.3. Preparation of (Bun4N)[{Ru(NO)(SC6HF4)2}2(
m
-SC6HF4)2(
m-
72H, (CH3)2CH), 2.78 (m, 8H, (CH3)2CH), 3.51 (m, 4H, (CH3)2CH),
OH)] ((Bun4N)[1])
6.91 (m, 4H, phenyl), 7.00 (s, 4H, phenyl) ppm. IR (KBr, cmꢀ1): 1818
[n(NeO)]. Anal. Calcd for C60H93NORuS4$CH2Cl2: C, 63.23; H, 8.26;
To a solution of Na(H2O)21 (40 mg, 0.029 mmol) in methanol
(2 mL) was added Bun4NBr (37 mg, 0.116 mmol) in water (3 mL). The
orange precipitate was washed with water (3 ꢁ 2 mL), dried in
vacuo, and recrystallized from CH2Cl2/hexanes. Yield: 43 mg (90%).
N, 1.21. Found: C, 63.13; H, 7.82; N, 1.28.
2.8. X-ray crystallography
1H NMR (400 MHz, acetone-d6):
d
¼ 0.19 (t, J ¼ 7.3 Hz, 12H,
Crystallographic data and experimental details for complexes
Na(H2O)21, (Ph4P)[1], and Na(H2O)22 are summarized in Table 1.
Intensity data were collected on a Bruker SMART APEX 1000 CCD
CH3CH2CH2CH2), 0.59e0.71 (m, 8H, CH3CH2CH2CH2), 1.00e1.10 (m,
8H, CH3CH2CH2CH2), 2.67 (t, J ¼ 8.4 Hz, 8H, CH3CH2CH2CH2), 4.40
(br. s, 1H, OH), 6.43e6.54 (m, 6H, phenyl) ppm. 19F NMR (376 MHz,
diffractometer using graphite-monochromated Mo-K
a radiation
acetone-d6):
d
¼ ꢀ142.04 (m, 16F), ꢀ130.39 (m, 8F) ppm. IR (KBr,
(
l
¼ 0.71073 Å). The data was corrected for absorption using the
cmꢀ1): 1867 [
n
(NeO)], 3448 [ (OeH)].
n
program SADABS. Structures were solved by direct methods and
refined by full-matrix least-squares on F2 using the SHELXTL soft-
ware package [9,10].
2.4. Preparation of (Ph4P)[{Ru(NO)(SC6HF4)2}2(m-SC6HF4)2(m-OH)]
((Ph4P)[1])
3. Results and discussion
To a solution of Na(H2O)21 (40 mg; 0.029 mmol) in methanol
(2 mL) was added Ph4PCl (43.5 mg, 0.116 mmol) in water (3 mL).
The orange precipitate was washed with water (3 ꢁ 2 mL).
Recrystallization from CH2Cl2/hexanes at room temperature affor-
ded orange crystals which were suitable for X-ray analysis. Yield:
3.1. Dinuclear hydroxo complexes
Treatment of Ru(NO)Cl3 with NaSR (R ¼ phenyl or 2,6-
dimethylphenyl) gave brown oily materials that did not crystal-
lize. On the other hand, the reaction of Ru(NO)Cl3 with NaSC6HF4
44 mg (90%). 1H NMR (400 MHz, acetone-d6):
d
¼ 4.40 (br. s, 1H,
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K.-W. Chan et al. / Journal of Organometallic Chemistry xxx (2016) 1e7
3
Table 1
Crystallographic data for Na(H2O)21, (Ph4P)[1] and Na(H2O)22.
Na(H2O)21$½CH2Cl2$¼H2O
(Ph4P)[1]
Na(H2O)22
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
C36.5H12.5ClF24N2NaO5.25Ru2S6
C60H26F24N2O3PRu2S6
1704.30
Triclinic
C24H58N3NaO6Ru3S7
1035.35
orthorhombic
Pbca
16.3711(3)
11.8249(4)
43.5556(11)
90
90
90
8431.8(4)
8
1.631
1471.92
Monoclinic
C2/c
25.2343(3)
14.8959(2)
28.0844(3)
90
93.2600(10)
90
10539.5(2)
8
P-1
14.9358(3)
16.6408(3)
25.0435(4)
90.3380(10)
92.6780(10)
96.1620(10)
6181.31(19)
4
1.831
173(2)
3356
7.204
b [Å]
c [Å]
a
b
g
, [ꢂ]
[ꢂ]
[ꢂ]
V [Å3]
Z
rcalcd [g cmꢀ1
Temp, K
F(000)
]
1.855
173(2)
5724
8.606
173(2)
4208
12.236
m
, mmꢀ1
Total reflection
Indep. reflection
Rint
20331
9221
0.0369
1.011
0.0310, 0.0585
0.0489, 0.0611
80436
23593
0.0370
1.011
0.0370, 0.0722
0.0511, 0.0758
16384
7791
0.0278
1.003
0.0390, 0.0949
0.0503, 0.0996
GoFa
Rb1, wRc2 (I > 2
s
(I))
R1, wR2 (all data)
(C6HF4 ¼ 2,3,5,6-tetrafluorophenyl) yielded a red crystalline prod-
uct, which was characterized as the dinuclear hydroxo complex
Na(H2O)2[Ru(NO)(SC6HF4)2]2(m-SC6HF4)
(m-OH)
(Na(H2O)21)
2
(Scheme 1). The hydroxo and aqua ligands were apparently derived
from the water of the reagents/solvent. In the 1H NMR spectrum, in
addition to the phenyl proton signals, two broad singlets at
and 2.87 ppm due to the hydroxo and aqua protons, respectively,
d
¼ 2.30
were observed. The IR spectrum displayed the
n(NeO) band at
1887 cmꢀ1, which is typical for linear nitrosyl ligand [11]. The
negative-ion FAB mass spectrum of Na(H2O)21 showed a peak at m/
z 1387 corresponding to [Mþ].
The solid-state structure of Na(H2O)21 is shown in Fig. 1.
Selected bond lengths and angles are listed in Table 2. The structure
consists of two pseudo octahedral Ru centers that are bridged by
two thiolates and one hydroxo ligand. In addition, each Ru binds to
two terminal thiolate and one nitrosyl ligand. The Ru2S2 ring adopts
a syn-exo conformation with an average RueSeRu angle of 78.73ꢂ.
The RueRu separation of 3.1598(4) Å indicates the absence of a
direct RueRu bond. The RueS distances for the bridging thiolate
ligands [av. 2.4910(8) Å] in 1 are longer than that in Cp*Ru(C6F5)(m-
S)(
m
-SC6F5)RuCp* [Cp* ¼ h5ꢀC5Me5; av. 2.295(1) Å] [12] because
the latter compound has a higher Ru oxidation state (þ3) and
contains a RueRu single bond. The RueS distances for the terminal
thiolate ligands [av. 2.3755(8) Å] are similar to that in
Fig. 1. Molecular structure of Na(H2O)21. Hydrogen atoms are omitted for clarity. The
ellipsoids are drawn at 30% probability level.
R
R
S
S
NO
Bun4NBr
ON
(Bun4N)[1]
Na(SC6HF4)
Ru
Ru
SR
Ru(NO)Cl3
S
Ph4PCl
S
F
OH
F
S
F
F
(Ph4P)[1]
OH2
F
F
F
Na
F
F
F
F
F
OH2
Na(H2O)21
R = C6HF4
Scheme 1. Synthesis of dinuclear Ru nitrosyl thiolate complexes.
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4
K.-W. Chan et al. / Journal of Organometallic Chemistry xxx (2016) 1e7
Table 2
Table 3
Selected bond lengths (Å) and angles (ꢂ) for Na(H2O)21 and (Ph4P)[1].
Selected bond lengths (Å) and angles (ꢂ) for Na(H2O)22.
Na(H2O)21
(Ph4P)[1]
Ru(1)-N(1)
Ru(1)-O(4)
Ru(1)-S(3)
Ru(1)-S(4)
Ru(1)-S(7)
Ru(1)-S(1)
Ru(2)-N(2)
Ru(2)-O(4)
1.730(4)
2.072(3)
Ru(2)-S(7)
Ru(3)-N(3)
Ru(3)-O(4)
Ru(3)-S(3)
Ru(3)-S(6)
Ru(3)-S(2)
Ru(3)-S(7)
Ru(1)-Ru(2)
2.4323(14)
1.724(4)
2.082(3)
Ru(1)-N(1)
Ru(1)-O(3)
Ru(1)-S(4)
Ru(1)-S(3)
Ru(1)-S(2)
Ru(1)-S(1)
Ru(2)-N(2)
Ru(2)-O(3)
Ru(2)-S(6)
Ru(2)-S(5)
Ru(2)-S(2)
Ru(2)-S(1)
Ru(1)-Ru(2)
Na(1)-O(3)
N(1)-Ru(1)-O(3)
N(1)-Ru(1)-S(4)
O(3)-Ru(1)-S(4)
N(1)-Ru(1)-S(3)
O(3)-Ru(1)-S(3)
S(4)-Ru(1)-S(3)
N(1)-Ru(1)-S(2)
O(3)-Ru(1)-S(2)
S(4)-Ru(1)-S(2)
S(3)-Ru(1)-S(2)
N(1)-Ru(1)-S(1)
O(3)-Ru(1)-S(1)
S(4)-Ru(1)-S(1)
S(3)-Ru(1)-S(1)
S(2)-Ru(1)-S(1)
N(2)-Ru(2)-O(3)
N(2)-Ru(2)-S(6)
O(3)-Ru(2)-S(6)
N(2)-Ru(2)-S(5)
O(3)-Ru(2)-S(5)
S(6)-Ru(2)-S(5)
N(2)-Ru(2)-S(2)
O(3)-Ru(2)-S(2)
S(6)-Ru(2)-S(2)
S(5)-Ru(2)-S(2)
N(2)-Ru(2)-S(1)
O(3)-Ru(2)-S(1)
S(6)-Ru(2)-S(1)
S(5)-Ru(2)-S(1)
S(2)-Ru(2)-S(1)
O(1)-N(1)-Ru(1)
O(2)-N(2)-Ru(2)
1.737(3)
2.062(2)
2.3727(9)
2.3768(9)
2.4757(8)
2.4969(9)
1.724(3)
2.057(2)
2.3671(8)
2.3851(9)
2.4939(8)
2.4975(8)
3.1598(4)
2.405(3)
176.13(13)
91.73(10)
87.08(6)
89.97(11)
86.44(7)
93.77(3)
105.59(10)
76.23(6)
160.20(3)
95.71(3)
106.98(11)
76.50(7)
81.75(3)
162.52(3)
84.02(3)
175.86(11)
91.44(10)
85.53(6)
90.24(10)
87.01(6)
91.31(3)
106.57(10)
75.90(6)
83.08(3)
162.34(3)
106.86(10)
76.57(6)
159.85(3)
96.85(3)
83.64(3)
172.4(3)
172.3(3)
1.721(3)
2.038(2)
2.3900(11)
2.4054(12)
2.4137(14)
2.4175(12)
1.716(4)
2.3957(12)
2.4012(11)
2.4126(13)
2.4207(13)
3.0452(5)
3.0626(4)
3.0617(5)
2.393(4)
2.3682(7)
2.3880(7)
2.5053(7)
2.5051(7)
1.725(2)
2.0401(19)
2.4109(9)
2.3573(8)
2.4879(8)
2.5111(7)
3.1560(3)
2.063(3)
Ru(2)-S(5)
Ru(2)-S(2)
Ru(2)-S(1)
2.4148(13)
2.4155(11)
2.4161(12)
177.62(16)
100.65(14)
78.45(9)
93.94(15)
88.12(9)
81.81(4)
102.73(15)
75.06(9)
86.72(4)
161.27(4)
99.48(14)
81.29(9)
159.50(4)
100.64(4)
85.13(4)
173.92(17)
97.46(16)
88.28(9)
98.72(15)
79.56(9)
86.44(4)
99.69(15)
81.48(9)
Ru(1)-Ru(3)
Ru(2)-Ru(3)
Na(1)-O(4)
N(1)-Ru(1)-O(4)
N(1)-Ru(1)-S(3)
O(4)-Ru(1)-S(3)
N(1)-Ru(1)-S(4)
O(4)-Ru(1)-S(4)
S(3)-Ru(1)-S(4)
N(1)-Ru(1)-S(7)
O(4)-Ru(1)-S(7)
S(3)-Ru(1)-S(7)
S(4)-Ru(1)-S(7)
N(1)-Ru(1)-S(1)
O(4)-Ru(1)-S(1)
S(3)-Ru(1)-S(1)
S(4)-Ru(1)-S(1)
S(7)-Ru(1)-S(1)
N(2)-Ru(2)-O(4)
N(2)-Ru(2)-S(5)
O(4)-Ru(2)-S(5)
N(2)-Ru(2)-S(2)
O(4)-Ru(2)-S(2)
S(5)-Ru(2)-S(2)
N(2)-Ru(2)-S(1)
O(4)-Ru(2)-S(1)
S(5)-Ru(2)-S(1)
S(2)-Ru(2)-S(1)
N(2)-Ru(2)-S(7)
O(4)-Ru(2)-S(7)
S(5)-Ru(2)-S(7)
S(2)-Ru(2)-S(7)
S(1)-Ru(2)-S(7)
N(3)-Ru(3)-O(4)
N(3)-Ru(3)-S(3)
O(4)-Ru(3)-S(3)
N(3)-Ru(3)-S(6)
O(4)-Ru(3)-S(6)
S(3)-Ru(3)-S(6)
N(3)-Ru(3)-S(2)
O(4)-Ru(3)-S(2)
S(3)-Ru(3)-S(2)
S(6)-Ru(3)-S(2)
N(3)-Ru(3)-S(7)
O(4)-Ru(3)-S(7)
S(3)-Ru(3)-S(7)
S(6)-Ru(3)-S(7)
S(2)-Ru(3)-S(7)
N(3)-Ru(3)-O(4)
Ru(1)-S(7)-Ru(3)
Ru(1)-S(7)-Ru(2)
Ru(3)-S(7)-Ru(2)
Ru(2)-O(4)-Ru(1)
Ru(2)-O(4)-Ru(3)
Ru(1)-O(4)-Ru(3)
74.78(9)
162.49(5)
86.16(4)
84.75(4)
175.62(15)
102.39(14)
78.12(9)
93.73(13)
90.65(8)
79.59(4)
100.07(14)
79.27(9)
157.36(4)
101.91(4)
100.93(14)
74.72(8)
86.44(4)
161.62(4)
86.49(4)
176.74(11)
92.16(9)
88.96(6)
87.69(9)
89.21(6)
92.40(3)
105.33(9)
77.84(6)
83.20(2)
166.36(3)
106.00(9)
73.31(6)
160.43(3)
95.50(3)
84.97(2)
177.60(10)
92.98(9)
85.56(6)
92.55(9)
85.41(6)
84.25(3)
103.27(9)
78.21(6)
163.76(3)
95.03(3)
108.78(9)
73.14(6)
89.47(3)
158.07(3)
85.21(2)
171.6(3)
173.8(2)
175.62(15)
78.62(4)
77.86(4)
78.23(4)
97.28(4)
160.56(4)
99.33(16)
94.86(11)
95.23(12)
95.01(12)
oxo compounds and clusters by redox-inactive metal cations is
well documented [16]. Fig. 2 shows that solid-state structure of
(Ph4P)[1]. Selected bond distances and angles are listed in Table 2.
The bond lengths of (Ph4P)[1] are similar to those in Na(H2O)21
except that the RueO distances are shortened by ca. 0.02 Å.
Cluster Na(H2O)21 is air-stable in both the solid state and solu-
tions in the dark. It is somewhat light-sensitive in solution, pre-
sumably due to the photolability of the nitrosyl ligands. Irradiation
of Na(H2O)21 in thf with UV light afforded a paramagnetic brown
material. The IR spectrum of this brown species showed the
disappearance of the NeO band at 1887 cmꢀ1, indicating the loss of
the NO ligands. The mass spectrum showed a peak at m/z 1109 that
can be assigned to {Ru2(SC6HF4)5}þ. Unfortunately, we have not
been able to crystallize this brown photo-product for further
characterization.
Ru(SC6F5)2(PPh3)2 (av. 2.334 Å) [13]. The nitrosyl groups are located
trans to the -hydroxo ligand and are essentially linear [av.
m
RueNeO angle of 172.4(3)ꢂ]. The IR NeO stretching frequency of
1865 cmꢀ1 is typical for linear nitrosyl complexes. The RueN dis-
tances in 1 [av. 1.729(3) Å] are shorter than that in trans-K2[Ru(N-
O2)4(OH)(NO)] (1.768(2) Å) [14], indicating that there is strong Ru-
to-NO backbonding 1 owing to the electron-releasing thiolate and
hydoxo ligands. The observed RueOH distances in 1 [av. 2.063 Å]
are shorter than that in [Ru4(m3-OMe)(m3-OH)(
2.149 Å) [15]. The {Na(H2O)2}þ moiety binds to the diruthenium
core via the -hydroxo ligand. In addition, dative bonds between Na
m-Br)2(CO)10] (av.
3.2. Trinuclear oxo-sulfido cluster
m
and three ortho fluorine atoms of the terminal thiolate ligands
[average NaeF distance of 2.526(3) Å] were observed.
Treatment of Ru(NO)Cl3 with 3 equivalents of NaSBut in thf
afforded the oxo-sulfido cluster Na(H2O)2[Ru(NO)(SBut)(
m-
As expected, the Naþ ion in Na(H2O)21 is labile and can be dis-
placed easily. Cation metathesis of Na(H2O)21 with Bun4NBr in
methanol afforded (Bun4N)[1]. Similarly, (Ph4P)[1] was prepared
from the metathesis of Na(H2O)21 with Ph4PCl. Upon substitution
of Bun4Nþ and Ph4Pþ for Naþ, the NeO stretching frequency in [1]ꢀ
decreases from 1887 cmꢀ1 to 1867 and 1865 cmꢀ1, respectively.
This result indicates the electron-withdrawing ability of the
{Na(H2O)2}þ moiety. The modulation of electron density of metal-
SBut)]3(m3-S)(m3-O) (Na(H2O)22) (Scheme 2). A trinuclear cluster
instead of dinuclear complex was formed possibly because the
electron-rich oxo and sulfido groups in Na(H2O)22 prefer to bind
with more metal centers. The oxo group was apparently derived
from the moisture in the reagents/solvent. The formation of sulfido
complexes/clusters via dealkylation of thiolate ligands is well pre-
cedented [17e22]. For example, the reaction of NbCl5 with NaSBut
afforded
the
sulfido
complexes
[Nb(S)(SBut)4]ꢀ
and
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K.-W. Chan et al. / Journal of Organometallic Chemistry xxx (2016) 1e7
5
Fig. 2. Molecular structure of (Ph4P)[1]. Hydrogen atoms are omitted for clarity. The ellipsoids are drawn at 30% probability level.
Scheme 2. Synthesis of the trinuclear oxo-sulfido clusters Na(H2O)22 and (Bun4N)[2].
[Nb(S)2(SBut)2]ꢀ [18]. Also, thermally induced CeS cleavage of
HOs3(CO)10 -SPh) led to the formation of trinuclear, tetranuclear
(m
and hexanuclear Os carbonyl sulfido clusters [22]. Therefore, we
believe that the formation of Na(H2O)22 involves the Ru-mediated
CeS bond cleavage of the ButSꢀ ligand. The resulting Ru]S inter-
mediate binds to two other Ru centers to afford the trinuclear Ru
sulfide. Also, deprotonation of a Ru aqua species gives RueOH that
binds to another Ru center to give a dinuclear Ru2(m-OH) inter-
mediate. Further deprotonation and coordination with another Ru
center yields the trinuclear Ru oxo product.
The 1H NMR spectrum of Na(H2O)22 displayed two singlets at
d
¼ 1.80 and 1.91 ppm due to the tert-butyl protons and a broad
peak at
d
¼ 3.02 ppm assignable to the aqua ligands. The nitrosyl
groups are inequivalent and three NeO bands at 1786, 1792 and
1801 cmꢀ1 appeared in the IR spectrum. The NeO stretching fre-
quencies for the oxo cluster Na(H2O)22 are significantly lower than
that for Na(H2O)21, owing to the p-donation of the oxo and sulfido
ligands [23]. The negative-ion FAB mass spectrum of Na(H2O)22
displayed a peak at m/z 967 corresponding to the molecular ion [Mþ
e S].
The solid-state structure of Na(H2O)22 has been established by
X-ray crystallography (Fig. 3). Selected bond lengths and angles are
listed in Table 3. It consists of an approximately planar {Ru3S3} core,
in which the three Ru centers are bridged by three thiolate ligands.
In addition, a m3-sulfido ligand and a m3-oxo ligand are located
above and below the Ru3 mean plane by 1.659 and 1.068 Å,
respectively. Each Ru is also coordinated to a linear nitrosyl
Fig. 3. Molecular structure of Na(H2O)22. Hydrogen atoms are omitted for clarity. The
ellipsoids are drawn at 30% probability level.
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6
K.-W. Chan et al. / Journal of Organometallic Chemistry xxx (2016) 1e7
(average of RueNeO angle of 177.93ꢂ) and a terminal thiolate
ligand. The RueRu distances [3.0452(5)e3.0626(4) Å] are rather
long, indicating the absence of direct RueRu interactions. The
RueS(thiolate) distances in the {Ru3S3} core [av. 2.408 Å] is shorter
4. Conclusions
In summary, ruthenium nitrosyl thiolate complexes have been
synthesized and structurally characterized. It was found that the
outcome of the reaction between Ru(NO)Cl3 and NaSR is dependent
on the steric and electronic factors of R. For R ¼ C6HF4, a dinuclear
hydroxo complex, Na(H2O)21, was formed. For R ¼ But, CeS cleav-
age of the thiolate ligand occurred and a trinuclear oxo-sulfido
cluster, Na(H2O)22 was obtained. The Naþ cation in Na(H2O)21
and Na(H2O)22 can be displaced by non-coordinating cations such
as Bun4Nþ and Ph4Pþ. For the reaction with the sterically bulky
than
that
in
cis-[Tp2Ru2(CO)2(m
-SBut)2]
[Tpꢀ ¼ hydridotris(pyrazolyl)borate; 2.4527(7) Å] [24]. The RueNO
distances [av. 1.723 Å] are comparable to those in Na(H2O)21 and
(Ph4P)[1]. The RueS(sulfido) distance in the range of 2.4137(14)e
2.4323(14)
Å
are longer those in [(Cp*Ru)3(m3-S)(m
-SPri)]
[2.280(2)e2.287(2) Å] [25]. The Ru-m3-O distances in 2ꢀ [av.
2.072 Å] are longer than the Ru-m2-O distances in dinuclear oxo
nitrosyl complexes such as [{RuCl2(NO)(dmpH)2}2(
[dmpH ¼ 3,5-dimethylpyrazole, 1.917(6) and 1.885(6) Å] and
[{Ru(bpb)(NO)}2(
m
-O)]
thiolate tippSꢀ,
a mononuclear thiolate-thiophenol complex,
Ru(NO)(Stipp)3(tippSH), was produced. The investigation of the
reactivity of these photoactive Ru nitrosyl thiolate complexes is
underway.
m
-O)] [H2bpb ¼ 1,2-bis(pyridine-2-carboximido)
benzene), 1.8829(3) Å] [23]. Unlike Na(H2O)21, the Na atom in
Na(H2O)22 is 5-coordinated. The {Na(H2O)2}þ moiety binds to the
triruthenium unit via the m-oxo ligand and two terminal thiolate
Acknowledgement
ligands. The NaeO(oxo) distance [2.393(4) Å] in Na(H2O)22 is
slightly shorter than the RueOH distance in Na(H2O)21. The NaeS
distances [av. 2.914 Å] are quite long, indicating that these in-
teractions are mostly dative in nature.
We thank the Hong Kong Research Grants Council (project no.
602913) and the Hong Kong University of Science and Technology
for support.
Similar to Na(H2O)21, the Naþ cation in Na(H2O)22 is
exchangeable. Metathesis of Na(H2O)22 with Bun4NBr in methanol
afforded (Bun4N)[2]. 1H NMR spectroscopy confirmed that the ratio
of Bun4Nþ to [2]ꢀ is 1:1. The NeO stretching frequencies of (Bun4N)
[2] (1752 and 1774 cmꢀ1) are lower than those in Na(H2O)22,
indicative of the electron-withdrawing ability of the {Na(H2O)2}þ
moiety.
Appendix A. Supplementary material
CCDC 1052828e1053830 contain the supplementary crystal-
lography data for Na(H2O)21, (Ph4P)[1] and Na(H2O)22 respectively.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
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3.3. Mononuclear nitrosyl complex
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j.jorganchem.2016.02.004