Synthesis and reactivity of hybrid phosphido- and hydrosulfido-bridged diruthenium complexes: Transformations into diruthenium and tetraruthenium complexes bridged by phosphido and sulfido ligands

Article abstract of DOI:10.1021/om3001247

The reaction of the monophosphido-bridged diruthenium(III) complex [Cp*RuCl(ν-PMe₂)(ν-Cl)RuClCp*] with sodium hydrogen sulfide affords the hybrid phosphido- and hydrosulfido-bridged diruthenium(III) complex [Cp*RuCl(ν-PMe₂)(ν-SH)RuClCp*]. The hydrosulfido-bridged diruthenium(III) complex can be further converted into the corresponding sulfido-bridged multinuclear ruthenium(III) complex via deprotonation of the hydrosulfido ligand. The hydrosulfido-bridged diruthenium(III) complex also reacts with bases to afford a coordinatively unsaturated diruthenium(III) complex, where insertion of terminal alkynes further occurs to form phosphido-bridged diruthenium(III) complexes bearing ruthenathiacyclobutene moieties.

Full text of DOI:10.1021/om3001247

Article
pubs.acs.org/Organometallics
Synthesis and Reactivity of Hybrid Phosphido- and Hydrosulfido-
Bridged Diruthenium Complexes: Transformations into Diruthenium
and Tetraruthenium Complexes Bridged by Phosphido and Sulfido
Ligands
Yoshihiro Miyake, Taichi Moriyama, Yoshiaki Tanabe, Satoshi Endo, and Yoshiaki Nishibayashi*
Institute of Engineering Innovation, School of Engineering, The University of Tokyo, Yayoi, Bunkyo-ku, Tokyo 113-8656, Japan
S
* Supporting Information
ABSTRACT: The reaction of the monophosphido-bridged diruthenium(III) complex [Cp*RuCl(μ-PMe2)(μ-Cl)RuClCp*]
with sodium hydrogen sulfide affords the hybrid phosphido- and hydrosulfido-bridged diruthenium(III) complex [Cp*RuCl-
(μ-PMe2)(μ-SH)RuClCp*]. The hydrosulfido-bridged diruthenium(III) complex can be further converted into the
corresponding sulfido-bridged multinuclear ruthenium(III) complex via deprotonation of the hydrosulfido ligand. The hydro-
sulfido-bridged diruthenium(III) complex also reacts with bases to afford a coordinatively unsaturated diruthenium(III) complex,
where insertion of terminal alkynes further occurs to form phosphido-bridged diruthenium(III) complexes bearing
ruthenathiacyclobutene moieties.
family of sulfur donor ligands, while hydrosulfido transition-
metal complexes are known to be convertible into sulfido com-
plexes via deprotonation of the hydrosulfido ligand.9 Herein, we
describe the preparation of a hybrid phosphido- and hydro-
sulfido-bridged diruthenium complex 2 from the reaction of 1,
as well as transformations of 2 into diruthenium and tetra-
ruthenium complexes bridged by phosphido and sulfido
ligands.
INTRODUCTION
■
Multimetallic complexes bridged by heteroatom ligands have
been developed as potentially useful catalysts for organic trans-
formations, where the nature of the bridging ligands is expected
to play an important role in the reactivity of multimetallic
complexes.1 We have already found a unique catalytic activity of
the alkanethiolato-bridged diruthenium complexes [Cp*RuCl-
(μ-SR)]2 (Cp* = η5-C5Me5)2,3 toward a variety of organic
transformations, including propargylic substitution reactions4
via ruthenium−allenylidene intermediates.5,6 More recently, we
have prepared the monophosphido-bridged diruthenium
complex [Cp*RuCl(μ-PMe2)(μ-Cl)RuClCp*] (1) and found
that its catalytic activity is different from that of [Cp*RuCl-
(μ-SR)]2.7 In addition, 1 is expected to work as a useful
precursor for diruthenium complexes bridged by different
heteroatoms, because 1 has a bridging chloride ligand which
may be easily substituted with a variety of heteroatom ligands.
In fact, we have succeeded in the preparation of a variety of
hybrid phosphido- and thiolato-bridged complexes [Cp*RuCl-
(μ-PMe2)(μ-SR)RuClCp*].8
RESULTS AND DISCUSSION
■
Treatment of 1 with 2 equiv of sodium hydrosulfide (NaSH) in
ethanol (EtOH) at room temperature for 18 h afforded the
corresponding hybrid phosphido- and hydrosulfido-bridged
diruthenium complex [Cp*RuCl(μ-PMe2)(μ-SH)RuClCp*]
(2) in 56% isolated yield (Scheme 1). The IR spectrum of 2
shows a weak ν(SH) band at 2459 cm−1, which is similar to that
of the dihydrosulfido-bridged diruthenium complex [Cp*RuCl-
(μ-SH)]2 (2462 cm−1).10 The 1H NMR spectrum of 2 displays
one doublet signal (JP−H = 0.8 Hz) at 4.16 ppm assignable to
the proton of the bridging hydrosulfido ligand, while the other 1H
NMR resonances due to Cp* moieties and dimethylphosphido
As an extension of our study on the preparation and reac-
tivity of diruthenium complexes, we have now envisaged to pre-
pare diruthenium complexes bridged by phosphido and hydro-
sulfido ligands. The hydrosulfido ligand (SH−) belongs to the
Received: February 15, 2012
Published: March 27, 2012
© 2012 American Chemical Society
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Article
positions, which is in accordance with the spectroscopic ob-
servations in solution. The interatomic distance between two
ruthenium atoms in 2 (2.8567(3) Å) is slightly shorter than
those in the phosphido- and thiolato-bridged diruthenium com-
plex [Cp*RuCl(μ-PMe2)(μ-SR)RuClCp*] (R = iPr, 2.8839(5) Å;
R = Ph, 2.86682(15) Å)8 but is in accord with generally known
Ru−Ru single-bond distances (2.71−3.02 Å).11 In addition, the
bond distances between ruthenium and sulfur (2.3003(6) Å)
and between ruthenium and phosphorus atoms (2.2924(6) Å)
are also similar to those in [Cp*RuCl(μ-PMe2)(μ-SR)-
RuClCp*].8
Scheme 1. Synthesis of 2
and hydrosulfido ligands appear with an intensity ratio of
30:6:1, showing that two Cp*Ru fragments are bridged by one
dimethylphosphido and one hydrosulfido ligand. Further-
1
more, H NMR resonances attributable to both the Cp* and
Complex 2 is expected to be transformed into the cor-
responding phosphido- and sulfido-bridged diruthenium com-
plexes via deprotonation of the hydrosulfido ligand. Treatment
of 2 with 1 equiv of NaN(SiMe3)2 in THF at room temperature
for 21 h gave the unprecedented cationic phosphido- and
sulfido-bridged tetraruthenium complex [{Cp*Ru(μ-PMe2)-
RuCp*}2(μ3-S)2(μ-Cl)]Cl (3·Cl) in 13% isolated yield (Scheme 2),
whose structure was confirmed by an X-ray analysis. An ORTEP
drawing of 3 is given in Figure 2. The bond distance between Ru(1)
and Ru(2) of Ru2PS cores in 3 (2.8451(8) Å) is slightly shorter
than that in 2 but is still in accord with generally known Ru−Ru
single-bond distances.11 On the other hand, the interatomic
distances of Ru(1)···Ru(1)* (3.7813(6) Å) and Ru(2)···Ru(2)*
(4.2070(5) Å) suggest no interaction between the corresponding
ruthenium atoms. The bond distances of Ru−P(1) (2.28 Å, mean)
and Ru−S(1) (2.35 Å, mean) within the Ru2PS cores in 3 are
comparable to those in [Cp*RuCl(μ-PMe2)(μ-SR)RuClCp*]8 and
2, while the sulfido ligands capping three ruthenium atoms
coordinate to the other ruthenium atoms in the neighboring Ru2PS
core at a slightly longer distance (Ru(1)−S(1)*, 2.4032(16) Å).
From the viewpoint of cluster chemistry, construction of complex 3
is quite unique, where the participation of phosphides, sulfides, and
chloride in bridging ruthenium atoms furnishes a rare tetraruthe-
nium core. The formation of 3 can be explained reasonably as
follows: elimination of hydrogen chloride from 2 should result in
the initial formation of the coordinatively unsaturated phosphido-
and sulfido-bridged diruthenium complex A bearing a Ru2PS core
in situ, followed by dimerization of A to give the tetraruthenium
complex 3, as described in Scheme 2.
dimethylphosphido ligands are observed to be split into a pair
of doublets, apparently arising from the sp3 hybridization on the
sulfur atom of the bridging hydrosulfido ligand, which creates
slightly different environments for the two Cp* and methyl
groups. The molecular structure of 2 was confirmed by an
X-ray analysis. As shown in the ORTEP drawing of 2 depicted
in Figure 1, the two Cp* ligands and two chloride ligands of 2
are located anti to each other, while the hydrogen atom of the
hydrosulfido ligand is disordered into two symmetrical
Figure 1. ORTEP drawing of 2. Hydrogen atoms, except for H(1), are
omitted for clarity. Selected interatomic distances (Å): Ru(1)−Ru(1)*,
2.8567(3); Ru(1)−Cl(1), 2.4603(6); Ru(1)−S(1), 2.3003(6); Ru(1)−
P(1), 2.2924(6); S(1)−H(1), 1.33(5).
Scheme 2. Deprotonation of 2 into Phosphido- and Sulfido-Bridged Complexes
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afforded the coordinatively unsaturated cationic phosphido- and
sulfido-bridged diruthenium complex [Cp*Ru(μ-PMe2)(μ-S)-
RuCp*][BArF ] (5·BArF ) in 73% isolated yield (Scheme 2).
4
4
The detailed structure of 5 was eventually confirmed by an X-
ray analysis using a single crystal of 5·PF6, which was obtained
by treatment analogous to that for 2 using NaPF6. An ORTEP
drawing of 5 is given in Figure 4. Complex 5 contains one
phosphido and one sulfido ligand, and both Cp* rings lie on a
horizontal axis, as shown in Figure 4. Corresponding to the
decrease in the formal number of Ru2 core electrons from 34 in
2 to 30 in 5, the interatomic distance between two ruthenium
atoms at 2.688(2) Å becomes slightly shorter than those
generally known for Ru−Ru single bonds11 but is rather longer
compared to those found in other coordinatively unsaturated
diruthenium complexes (2.53−2.66 Å).12 The bond distances
of Ru−P(1) (2.28 Å, mean) in 5 are comparable to those in the
phosphido- and sulfido-bridged complexes 2−4, while those of
Ru−S(1) (2.20 Å, mean) are fairly shorter than those in
complexes 2−4, as the two ruthenium atoms in 5 are connected
strongly by the bridging sulfido ligand having delocalized
Ru−S−Ru multiple bonding.13
Figure 2. ORTEP drawing of the cationic part of 3·Cl·2C4H8O.
Hydrogen atoms are omitted for clarity. Selected interatomic distances
(Å): Ru(1)−Ru(2), 2.8451(8); Ru(2)−Cl(1), 2.4115(14); Ru(1)−
S(1), 2.3611(19); Ru(1)−S(1)*, 2.4032(16); Ru(2)−S(1),
2.3321(18); Ru(1)−P(1), 2.273(2); Ru(2)−P(1), 2.293(2);
Ru(1)···Ru(1)*, 3.7813(6); Ru(2)···Ru(2)*, 4.2070(5).
When 2 was reacted with 1 equiv of NaN(SiMe3)2 in the
presence of 2 equiv of tert-butyl isocyanide in THF at −78 °C
and the solution was warmed slowly to room temperature with
further stirring for 7 h, the cationic bis(isonitrile) diruthenium
complex [Cp*Ru(CNtBu)(μ-PMe2)(μ-S)Ru(CNtBu)Cp*]Cl
(4·Cl) was obtained in 33% isolated yield (Scheme 2). This
result also indicates the formation of a coordinatively
unsaturated phosphido- and sulfido-bridged diruthenium
complex like A in situ, whose vacant sites are subsequently
filled by isocyanide. An X-ray crystallographic study has also
confirmed the molecular structure of 4, whose ORTEP drawing
is shown in Figure 3. The bond distances of Ru(1)−Ru(2)
(2.8703(13) Å), Ru−P(1) (2.28 Å, mean), and Ru−S(1) (2.34 Å,
mean), which are close to those in 2, indicate that the phosphido-
and sulfido-bridged complex 4 has also a Ru2PS core similar to
that of the phosphido- and hydrosulfido-bridged complex 2.
Figure 4. ORTEP drawing of the cationic part of 5·PF6. Hydrogen
atoms are omitted for clarity. Selected interatomic distances (Å):
Ru(1)−Ru(2), 2.688(2); Ru(1)−S(1), 2.198(6); Ru(2)−S(1),
2.208(6); Ru(1)−P(1), 2.288(5); Ru(2)−P(1), 2.264(5).
As the formation of unsaturated Ru2PS species in situ was
confirmed by the isolation of 5, we next investigated reactions
with terminal alkynes. Unfortunately, all these diruthenium
complexes did not work as catalysts toward the propargylic
substitution reactions so far described by our group.4,6 Stoichio-
metric reactions of these diruthenium complexes with terminal
alkynes revealed that neither the corresponding vinylidene nor
alkyne complexes were formed,14 but insertion of terminal
alkynes into the Ru−S bond was found to occur for some
diruthenium complexes such as 2 and 5·BArF . When the
4
reaction of 2 with 1 equiv of phenylacetylene was carried out in
the presence of 1 equiv of triethylamine in dichloromethane
at room temperature for 15 h, [Cp*Ru{μ3-SC(Ph)C(H)}-
(μ-PMe2)RuCp*]Cl (6·Cl) was obtained in 61% isolated
yield (Scheme 3a). Separately, we confirmed that reaction of
Figure 3. ORTEP drawing of the cationic part of 4·Cl. Hydrogen
atoms are omitted for clarity. Selected interatomic distances (Å):
Ru(1)−Ru(2), 2.8703(13); Ru(1)−S(1), 2.345(4); Ru(2)−S(1),
2.331(3); Ru(1)−P(1), 2.287(3); Ru(2)−P(1), 2.277(4).
5·BArF with 1 equiv of phenylacetylene under similar
4
As expected, a coordinatively unsaturated complex was
isolated by the reaction of 2 with a stoichiometric amount of
bases. Treatment of 2 with 1 equiv of triethylamine in the
presence of 1 equiv of sodium tetrakis(3,5-bis(trifluoromethyl)-
conditions also proceeded smoothly to give the corresponding
diruthenium complex 6·BArF4 in 87% yield (Scheme 3b). These
results indicate that the coordinatively unsaturated cationic
complex 5 should be a reactive intermediate in the conversion
of 2 into 6, where the subsequent step is the formation of the
phenyl)borate (NaBArF ) in THF at room temperature for 16 h
4
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Scheme 3. Reaction of 2 and 5·BArF4 with Terminal Alkynes
2.233(3) Å). The two ruthenium atoms also connect to each
other by a Ru−Ru single bond at a distance of 2.7254(4) Å.
The C(1)−C(2) bond length at 1.393(4) Å is intermediate
between the typical C−C single- and double-bond distances15
and is comparable to those in the π-bonded alkenethiolato
ligands of [Cp*Ir{μ-SC(Me)CHCH2COMe}]2[BF4]2
(1.392(9) Å)16 and [(Cp*Ru)2(CpTi)2Pd2(PPh3)(μ3-S)3(μ2-O)-
{μ3-SC(COOMe)CCOOMe}] (1.401(9) Å),17 while the
Ru(1)−C(1) and S(1)−C(2) distances at 2.023(4) and
1.772(3) Å, respectively, in 6 are comparable to those for
Ru−C and S−C single bonds. The torsion angles of S(1)−
Ru(1)−C(1)−C(2) (7.90(11)°) and Ru(1)−S(1)−C(2)−C(3)
(−164.21(18)°) indicate that five atoms (Ru(1), C(1), C(2),
C(3), and S(1)) are nearly coplanar. Furthermore, the sum of the
three bond angles around C(2) associated with three atoms is
359.4°, indicating that the C(2) atom is essentially of sp2
character.
Moreover, the reaction of 2 with 1 equiv of 1-phenyl-2-
propyn-1-ol in the presence of triethylamine in THF at room
temperature also afforded the corresponding cationic phosphi-
do-bridged diruthenium complex bearing a ruthenathiacyclo-
butene moiety [Cp*Ru{μ3-SC(CH(OH)Ph)C(H)}-
(μ-PMe2)RuCp*]Cl (7·Cl) in 37% isolated yield (Scheme 3a).
The molecular structure of 7 was also confirmed by an X-ray
study and is found to be similar to that of 6 (Figure 6). In this
reaction, no formation of the allenylidene complex was
observed.
π-alkyne complex B by the reaction of 5 with the alkyne,
followed by an insertion of the alkyne into one Ru−S bond to
give 6 (Scheme 4). The regioselective formation of 6 is a result
of steric repulsion between the Cp* ring and the substituent on
the terminal alkyne.
Scheme 4. Formation of 6
The molecular structure of 6 was confirmed by an X-ray
analysis of 6·Cl. As shown by the ORTEP drawing of 6 in
Figure 5, the phenylacetylene molecule has been inserted into
one of the Ru−S bonds to form a ruthenathiacyclobutene
segment (S(1)−Ru(1)−C(1)−C(2)), and the resultant CC
moiety coordinates to the other ruthenium atom in a η2 manner
at the same time (Ru(2)−C(1), 2.155(3) Å; Ru(2)−C(2),
Figure 6. ORTEP drawing of the cationic part of 7·Cl. Hydrogen
atoms are omitted for clarity. Selected interatomic distances (Å):
Ru(1)−Ru(2), 2.7230(13); Ru(1)−S(1), 2.455(2); Ru(2)−S(1),
2.424(2); Ru(1)−P(1), 2.247(3); Ru(2)−P(1), 2.3263(19); Ru(1)−
C(1), 2.027(7); Ru(2)−C(1), 2.136(7); Ru(2)−C(2), 2.236(7);
S(1)−C(2), 1.777(7); C(1)−C(2); 1.408(10), C(2)−C(3),
1.495(10). Selected interatomic angles (deg): S(1)−C(2)−C(1),
105.2(5); S(1)−C(2)−C(3), 121.5(5); C(1)−C(2)−C(3), 132.7(7).
It must be noted that the use of transition-metal complexes
for the formation of carbon−sulfur bonds has recently attracted
much attention in the organosulfur chemistry, and the insertion
of unsaturated compounds such as alkynes into sulfur−sulfur or
sulfur−metal bonds has also been developed as a tool for the
formation of carbon−sulfur bonds.18 However, examples of the
reaction of a hydrosulfido- or sulfido-bridged diruthenium com-
plex as a sulfur source with alkynes to form carbon−sulfur
bonds are still limited in number, and reactions from
bis(thiolato)- and bis(sulfido)-bridged diruthenium precursors
are reported to undergo insertion of alkynes into metal−sulfur
Figure 5. ORTEP drawing of the cationic part of 6·Cl·ClCH2CH2Cl.
Hydrogen atoms are omitted for clarity. Selected interatomic distances
(Å): Ru(1)−Ru(2), 2.7254(4); Ru(1)−S(1), 2.4459(8) ; Ru(2)−S(1),
2.4282(8); Ru(1)−P(1), 2.2548(9); Ru(2)−P(1), 2.3401(10);
Ru(1)−C(1), 2.023(4); Ru(2)−C(1), 2.155(3); Ru(2)−C(2),
2.233(3); S(1)−C(2), 1.772(3); C(1)−C(2), 1.393(4); C(2)−C(3),
1.481(5). Selected interatomic angles (deg): S(1)−C(2)−C(1),
104.6(3); S(1)−C(2)−C(3), 121.72(19); C(1)−C(2)−C(3),
133.1(3).
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Table 1. Crystallographic Data for 2, 3·Cl·2THF, and 4·Cl
2
3·Cl·2C4H8O
4·Cl
chem formula
formula wt
cryst size, mm3
cryst color, habit
cryst syst
space group
a, Å
C22H37Cl2PRu2S
637.61
C52H88Cl2O2P2Ru4S2
1346.52
C32H54ClN2PRu2S
767.42
0.35 × 0.25 × 0.15
brown, block
monoclinic
C2/c (No. 15)
16.5909(6)
8.5787(4)
18.0461(7)
90
0.40 × 0.20 × 0.20
dark brown, block
monoclinic
C2/c (No. 15)
13.9721(8)
17.8282(13)
22.6549(13)
90
0.20 × 0.15 × 0.05
red, platelet
monoclinic
P21/n (No. 14)
20.4886(12)
8.3947(6)
22.4029(13)
90
b, Å
c, Å
α, deg
β, deg
108.6524(12)
90
97.0320(16)
90
113.4147(14)
90
γ, deg
V, Å3
2433.58(16)
4
5600.8(6)
4
3535.9(4)
4
Z
D
calcd, g cm−3
1.740
1.597
1.441
F(000)
μcalcd, cm−1
1288
2752
1584
16.198
13.227
10.569
transmissn factor range
no. of measd rflns
no. of unique rflns
Rint
0.670−0.784
11 476
0.606−0.768
27 110
0.328−0.949
25 873
2767
6398
7751
0.0266
0.0309
0.1735
no. of refined params
204
307
406
a
R1 (I > 2σ(I))
0.0175
0.0494
0.0682
b
wR2 (all data)
0.0444
0.1522
0.2134
max/min residual peaks (e/Å3)
+0.47/−0.37
+2.04/−1.16
+7.63/−2.96
a
b
R1 = ∑||Fo| − |Fc||/∑|Fo|. wR2 = [∑(w(Fo2 − Fc2)2)/∑w(Fo )2]1/2; w = 4Fo /[pFo2 + qσ(Fo )]; p = 0 (2, 3·Cl·2C4H8O), 0.001 (4·Cl); q = 1.072
(2), 10.4 (3·Cl·2C4H8O), 0.598 (4·Cl).
2
2
2
bonds so far.19,20 Now we have succeeded in demonstrating
that the monosulfido-bridged diruthenium(III) species also
allow the insertion of alkynes into one of the metal−sulfur
bonds. The incorporation of the electron-rich phosphido
bridging ligand into the electron-poor diruthenium(III) core
may presumably contribute to the formation of electron-
deficient but slightly stable coordinatively unsaturated
diruthenium species and may have brought about the novel
reactivity with alkynes.
In summary, a hybrid phosphido- and hydrosulfido-bridged
diruthenium(III) complex was newly prepared from a mono-
phosphido-bridged diruthenium complex. The hydrosulfido-
bridged diruthenium(III) complex was further converted into
the corresponding sulfido-bridged multinuclear ruthenium(III)
complexes via deprotonation of the hydrosulfido ligand. The
reaction of hydrosulfido-bridged diruthenium(III) complexes
with terminal alkynes in the presence of a base gave phosphido-
bridged diruthenium(III) complexes bearing ruthenathiacyclo-
butene moieties. This is a unique example of monosulfido-
bridged diruthenium(III) species participating in the insertion
of alkynes to Ru−S to form C−S, where the electron-rich
phosphido ligand may be also engaged.
complex [Cp*RuCl(μ-PMe2)(μ-Cl)RuClCp*] (1) was prepared
according to the literature procedures.7
Preparation of 2, a Phosphido- and Hydrosulfido-Bridged
Diruthenium(III) Complex. To a solution of NaSH (50.4 mg, 0.899
mmol) in ethanol (3 mL) was added a solution of [Cp*RuCl-
(μ-PMe2)(μ-Cl)RuClCp*] (1; 286.5 mg, 0.448 mmol) in ethanol
(5 mL), and the mixture was stirred at room temperature for 18 h. The
solvent was removed under reduced pressure, and the residue was
extracted with toluene (10 mL). The extract was filtered through
Celite under a nitrogen atmosphere, and the filtrate was concentrated
under reduced pressure. The obtained residue was recrystallized from
toluene−n-hexane to give brown block crystals of [Cp*RuCl-
(μ-PMe2)(μ-SH)RuClCp*] (2; 159.3 mg, 0.250 mmol, 56%). 1H
NMR (C6D6): δ 1.52 (d, 15H, JP−H = 1.1 Hz), 1.62 (d, 15H, JP−H = 1.1
Hz), 2.03 (d, 3H, JP−H = 11.3 Hz), 2.05 (d, 3H, JP−H = 11.3 Hz), 4.16 (d,
1H, JP−H = 0.8 Hz). 31P{1H} NMR (C6D6): δ 252.2 (s). IR (KBr, cm−1):
2459 (S−H). Anal. Calcd for C22H37Cl2PRu2S: C, 41.44; H, 5.85.
Found: C, 41.50; H, 5.74.
Preparation of 3·Cl, a Cationic Phosphido- and Sulfido-
Bridged Tetraruthenium(III) Complex. To a solution of 2 (63.7
mg, 0.100 mmol) in THF (1 mL) was added a solution of
NaN(SiMe3)2 (18.2 mg, 0.0993 mmol) in THF (1 mL), and the
mixture was stirred at room temperature for 21 h. After the removal of
the solvent under reduced pressure, the residue was washed with n-
hexane and then recrystallized from THF−n-hexane to give dark
brown block crystals of [{Cp*Ru(μ-PMe2)RuCp*}2(μ3-S)2(μ-Cl)]-
Cl·2C4H8O (3·Cl·2C4H8O), which were further collected and dried in
EXPERIMENTAL SECTION
■
General Methods. 1H NMR (270 MHz) and 31P NMR (109
MHz) spectra were recorded on a JEOL Excalibur 270 spectrometer in
suitable solvents. IR spectra were recorded on a JASCO FT/IR 4100
Fourier transform infrared spectrophotometer. Elemental analyses
were performed at the Microanalytical Center of The University of
Tokyo. Mass spectra were measured on a JEOL Accu TOF JMS-
T100LP mass spectrometer. All reactions were carried out under a dry
nitrogen atmosphere. Solvents were dried by the usual methods and
distilled before use. The monophosphido-bridged diruthenium
vacuo to give 3·Cl (7.4 mg, 0.0063 mmol, 13%). H NMR (THF-d8):
1
δ 1.19 (d, 6H, JP−H = 11.6 Hz), 1.58 (s, 30H), 1.89 (s, 30H), 2.05 (d,
6H, JP−H = 10.5 Hz). 31P{1H} NMR (THF-d8): δ 210.7 (s). HRMS
(ESI-TOF): calcd for C44H72ClP2Ru4S2 [3] 1169.03823, found
1169.03604.
Preparation of 4·Cl, a Cationic Phosphido- and Sulfido-
Bridged Bis(isonitrile) Diruthenium(III) Complex. To a solution
t
of 2 (64.5 mg, 0.101 mmol) and BuNC (16.9 mg, 0.203 mmol) in
THF (5 mL) at −78 °C was added a solution of NaN(SiMe3)2 (18.5 mg,
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of 5·PF6 suitable for an X-ray analysis were obtained by the analogous
Table 2. Crystallographic Data for 5·PF6, 6·Cl·ClCH2CH2Cl,
and 7·Cl
1
reaction of 2 with NaPF6. H NMR (THF-d8): δ 1.92 (s, 30H), 2.58
(d, 15H, JP−H = 11.3 Hz), 7.58 (br s, 4H), 7.80 (br s, 8H). 31P{1H}
NMR (THF-d8): δ 260.9 (s). Anal. Calcd for C54H48BF24PRu2S: C,
45.39; H, 3.39. Found: C, 44.99; H, 3.34.
5·PF6
6·Cl·ClCH2CH2Cl
7·Cl
chem
formula
C22H36F6P2Ru2S
C32H46Cl3PRu2S
C31H44ClOPRu2S
Preparation of 6·Cl, a Cationic Phosphido- and Vinyl-
thiolato-Bridged Diruthenium(III) Complex with Phenylacety-
lene Inserted. To a solution of 2 (96.1 mg, 0.151 mmol) in
dichloromethane (15 mL) were added phenylacetylene (15.6 mg,
0.153 mmol) and triethylamine (15.2 mg, 0.150 mmol), and the
mixture was stirred at room temperature for 15 h. The solvent was
removed under reduced pressure, and the residue was extracted with
toluene (20 mL). The extract was filtered through Celite under a
nitrogen atmosphere, and the filtrate was concentrated under reduced
pressure. The obtained residue was recrystallized from 1,2-dichloro-
ethane−diethyl ether to give orange plate crystals of [Cp*Ru(μ3-
SCPhCH)(μ-PMe2)RuCp*]Cl·C2H4Cl2 (6·Cl·ClCH2CH2Cl),
which were collected and dried in vacuo to give 6·Cl (64.6 mg,
0.0919 mmol, 61%). 1H NMR (CD2Cl2): δ 1.68 (br d, 30H, JP−H = 1.6
Hz), 2.08 (d, 3H, JP−H = 11.1 Hz), 2.25 (d, 3H, JP−H = 10.8 Hz), 6.99
(br, 1H), 7.47 (br, 3H), 7.90 (br, 1H), 9.45 (s, 1H). 31P{1H} NMR
(CD2Cl2): δ 206.8 (s). Anal. Calcd for C30H42ClPRu2S: C, 51.23; H,
6.02. Found: C, 50.75; H, 6.06.
formula wt
710.66
802.25
733.31
cryst size,
mm3
0.10 × 0.10 ×
0.05
0.36 × 0.34 × 0.05 0.10 × 0.05 × 0.01
cryst color,
habit
dark brown,
platelet
orange, plate
red, chunk
cryst syst
triclinic
monoclinic
P21/c (No. 14)
13.4501(5)
14.0500(5)
19.3656(6)
90
orthorhombic
Pna21 (No. 33)
14.0370(7)
19.5485(9)
11.3344(5)
90
space group P1 (No. 2)
̅
a, Å
8.629(2)
10.694(3)
14.922(3)
80.105(5)
87.814(6)
89.707(7)
1355.5(6)
2
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
Z
108.9440(8)
90
90
90
3461.4(2)
4
3110.2(3)
4
D
calcd, g cm−3 1.741
1.539
1.566
Preparation of 7·Cl, a Cationic Phosphido- and Vinyl-
thiolato-Bridged Diruthenium(III) Complex with Propargylic
Alcohol Inserted. To a solution of 2 (31.9 mg, 0.0500 mmol) in
THF (5 mL) were added 1-phenyl-2-propyn-1-ol (6.6 mg, 0.050
mmol) and triethylamine (5.1 mg, 0.050 mmol), and the mixture was
stirred at room temperature for 2 h. The mixture was filtered through
Celite under a nitrogen atmosphere, and the filtrate was concentrated
under reduced pressure. The obtained residue was recrystallized from
CH2Cl2−diethyl ether to give red crystals of [Cp*Ru{μ3-SC(CH-
(OH)Ph)CH}(μ-PMe2)RuCp*]Cl (7·Cl·CH2Cl2; 15.0 mg, 0.018
mmol, 37%). Red chunk crystals of 7·Cl suitable for an X-ray analysis
were obtained by further recrystallization from THF−diethyl ether. 1H
F(000)
μcalcd, cm−1
712
1632
1496
13.602
12.310
11.984
transmissn
factor range
0.313−0.934
0.675−0.940
0.290−0.988
no. of measd 13016
rflns
31751
7891
25901
6892
no. of unique 5964
rflns
Rint
0.1471
0.0529
398
0.0836
379
no. of refined 327
params
R1 (I >
2σ(I))
0.1079
0.0394
0.0650
a
NMR (CD2Cl2): δ 1.73 (d, 15H, JP−H = 1.6 Hz), 1.77 (d, 15H, JP−H
=
1.4 Hz), 1.97 (d, 3H, JP−H = 10.8 Hz), 2.16 (d, 3H, JP−H = 10.5 Hz),
4.73 (s, 1H), 6.60 (br s, 1H), 7.31 (d, 1H, J = 7.0 Hz), 7.38−7.44 (m,
2H), 7.70 (d, 2H, J = 7.0 Hz), 9.41 (s, 1H). 31P{1H} NMR (CD2Cl2):
δ 204.5 (s). Anal. Calcd for C32H46Cl3OPRu2S: C, 46.97; H, 5.67.
Found: C, 46.74; H, 5.72.
wR2 (all
0.2342
0.0705
0.1089
b
data)
max/min
residual
peaks
+3.45/−5.33
+1.01/−1.06
+3.23/−2.63
(e/Å3)
X-ray Diffraction Studies. Diffraction data for 2, 3·Cl·2C4H8O,
4·Cl, 5·PF6, 6·Cl·ClCH2CH2Cl, and 7·Cl were collected for the 2θ
range of 6−55° at −100 °C on a Rigaku R-AXIS RAPID imaging plate
area detector with graphite-monochromated Mo Kα (λ = 0.710 75 Å)
radiation, with VariMax optics for 6·Cl·ClCH2CH2Cl and 7·Cl.
Intensity data were corrected for empirical absorptions (ABSCOR)
and for Lorentz and polarization effects. The structure solutions and
refinements were carried out by using the CrystalStructure package.21
The positions of non-hydrogen atoms were determined by direct
methods (SHELXS-97 for 2, SIR-92 for 3·Cl·2C4H8O, SIR-97 for
4·Cl, 6·Cl·ClCH2CH2Cl, and 7·Cl) or heavy-atom Patterson methods
(PATTY for 5·PF6) and subsequent Fourier syntheses (DIRDIFF-
a
b
2
R1 = ∑||Fo| − |Fc||/∑|Fo|. wR2 = [∑(w(Fo2 − Fc2)2)/∑w(Fo )2]1/2
;
2
2
w = 4Fo /qσ(Fo ); q = 1.407 (5·PF6), 2.93 (6·Cl·ClCH2CH2Cl), 2.29
(7·Cl).
0.101 mmol) in THF (5 mL). The reaction mixture was warmed to
room temperature and stirred for 7 h. After the removal of the solvent
under reduced pressure, the residue was washed with n-hexane and
diethyl ether and was extracted with THF (5 mL). The extract was
filtered through Celite under a nitrogen atmosphere, and the filtrate
was concentrated under reduced pressure. The residue was recrystallized
from THF−diethyl ether to give red platelet crystals of [Cp*Ru(CNtBu)-
(μ-PMe2)(μ-S)Ru(CNtBu)Cp*]Cl (4·Cl; 25.4 mg, 0.0331 mmol, 33%).
1H NMR (THF-d8): δ 1.45 (s, 18H), 1.87 (d, 30H, JP−H = 0.81 Hz), 2.30
(d, 3H, JP−H = 11.3 Hz), 2.31 (d, 3H, JP−H = 11.6 Hz). 31P{1H} NMR
(THF-d8): δ 196.8 (s). Anal. Calcd for C32H54ClN2PRu2S: C, 50.08; H,
7.09; N, 3.65. Found: C, 49.93; H, 7.17; N, 3.60.
99)22 and were refined on Fo using all the unique reflections by full-
2
matrix least squares with anisotropic thermal parameters except for the
chlorine, oxygen, and carbon atoms (Cl(3), O(1), O(2), C(23),
C(24), C(25)) which comprise the disordered chloride and THF in
3·Cl·2C4H8O and two Cp* carbon atoms (C(1) and C(2)) in 5·PF6.
The position of the hydrogen atom (H(1)) of the bridging
hydrosulfido ligand in 2 was located from the difference Fourier
synthesis and was further refined with an atom occupancy of 0.5,
where the sulfur atom S(1) is located at a symmetric position. The
counteranionic chlorine atom in 3·Cl·2C4H8O is heavily disordered
and was solved as a mixture of two chlorine atoms (Cl(2) and Cl(3))
with atom occupancies of 0.425 and 0.15 (in a symmetric position),
respectively. The oxygen and carbon atoms of the THF molecule in
3·Cl·2C4H8O are heavily disordered between two positions and were
solved as oxygen atoms (O(1) and O(2)) with atom occupancies of
0.875; thus, the hydrogen atoms of the THF molecule were not
located. All other hydrogen atoms were placed at calculated
Preparation of 5·BArF , a Coordinatively Unsaturated
4
Cationic Phosphido- and Sulfido-Bridged Diruthenium(III)
Complex. To a solution of 2 (64.6 mg, 0.101 mmol) and tri-
ethylamine (15 μL, 0.11 mmol) in THF (10 mL) was added sodium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (NaBArF ) (91.2 mg,
4
0.103 mmol), and the mixture was stirred at room temperature for
16 h. The resultant solution was filtered through Celite under a
nitrogen atmosphere, and the filtrate was concentrated under reduced
pressure. The residue was recrystallized from THF−n-hexane to give a
dark brown crystalline solid of [Cp*Ru(μ-PMe2)(μ-S)RuCp*][BArF ]
4
(5·BArF ; 106.1 mg, 0.0743 mmol, 73%). Dark brown platelet crystals
4
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Organometallics
Article
positions with fixed isotropic parameters. The goodness of fit indicator
[∑w(|Fo| −|Fc|)2/(Nobservns − Nparams)]1/2 was refined to a value of 1.000
for all the compounds. The Flack parameter was refined to a value of
0.11(5) for 7·Cl. Anomalous dispersion effects were included in Fc, and
neutral atom scattering factors and the values for Δf ′ and Δf ″ were taken
from ref 23. Details of the crystal and data collection parameters are
summarized in Tables 1 and 2.
(e) Winter, R. F.; Zalis, S. Coord. Chem. Rev. 2004, 248, 1565.
́
(f) Rigaunt, S.; Touchard, D.; Dixneuf, P. H. Coord. Chem. Rev. 2004,
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(6) For our recent examples, see: (a) Yamauchi, Y.; Yuki, M.;
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Chem. Soc. 2008, 130, 2908. (b) Daini, M.; Yoshikawa, M.; Inada, Y.;
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(7) Miyake, Y.; Endo, S; Nomaguchi, Y.; Yuki, M.; Nishibayashi, Y.
Organometallics 2008, 27, 4017.
(8) Miyake, Y.; Endo, S; Yuki, M.; Tanabe, Y.; Nishibayashi, Y.
Organometallics 2008, 27, 6039.
(9) For reviews on hydrosulfido complexes of transition metals and
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S.; Hidai, M. Coord. Chem. Rev. 2001, 213, 211. (b) Peruzzini, M.; de
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ASSOCIATED CONTENT
* Supporting Information
■
S
CIF files giving crystallographic data for 2, 3·Cl·2C4H8O, 4·Cl,
5·Cl, 6·Cl·ClCH2CH2Cl, and 7·Cl. This material is available
free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: ynishiba@sogo.t.u-tokyo.ac.jp.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the Funding Program for Next
Generation World-Leading Researchers (GR025) and a Grant-
in-Aid for Young Scientists (B) (No. 21750088) from the
Ministry of Education, Culture, Sports, Science and Tech-
nologyof Japan. T.M. acknowledges the Global COE program
for Chemistry Innovation. We thank the Research Hub for
Advanced Nano Characterization at The University of Tokyo
for X-ray analyses.
(11) Gao, Y.; Jennings, M. C.; Puddephatt, R. J.; Jenkins, H. A.
Organometallics 2001, 20, 3500 and references therein.
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