Ruthenium complexes with an anthyridine-based ligand. Synthesis, characterization and catalytic activity

Article abstract of DOI:10.1002/jccs.201300084

Complexation of 2, 7-bis(2-pyridinyl)-9-phenylanthyridine (4) with [RuCl₂(CO)₃(THF)] and [(η⁶-p-cy-mene) RuCl₂]₂ provided the mono-nuclear complex [(4)Ru(CO) ₃Cl][RuCl₃(CO)₃

Full text of DOI:10.1002/jccs.201300084

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Ruthenium Complexes with an Anthyridine-based Ligand. Synthesis, Characterization
and Catalytic Activity
Ying-Hao Lo, Yi-Hung Liu, Shie-Ming Peng and Shiuh-Tzung Liu*
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, ROC
(Received: Feb. 5, 2013; Accepted: Mar. 12, 2013; Published Online: Apr. 15, 2013; DOI: 10.1002/jccs.201300084)
Complexation of 2,7-bis(2-pyridinyl)-9-phenylanthyridine (4) with [RuCl2(CO)3(THF)] and [(h6-p-cy-
mene)RuCl2]2 provided the mono-nuclear complex [(4)Ru(CO)3Cl][RuCl3(CO)3] (5) and the dinuclear
complex [(4)Ru2(p-cymene)2Cl2] (6), respectively. Both complexes have been characterized by spectro-
scopic, elemental and crystallographic analyses. Complex 6 is an efficient catalyst for the oxidative
cyanation of various tertiary arylamines.
Keywords: Ruthenium; Anthyridine; Cyanation.
INTRODUCTION
Bimetallic complexes with the metal centers in close
3,5-pyridinedicarboxaldehyde 3, which then underwent
the condensation reaction with 2-acetylpyridine to give the
desired anthyridine ligand 4. Compound 4 was character-
ized by NMR spectroscopy.
proximity have received much attention due to the possible
synergistic effect between the metal ions.1-4 In this context,
the ligand design for the accommodation of two metal ions
in close proximity play a key role for the study. Among var-
ious ligand systems, we have been working on the develop-
ment of naphthyridine-based ligands (Scheme I), which are
suitable for building the corresponding dimetallic sys-
tems.4 Unlike naphthyridine, anthyridine-based ligands are
less explored,5 which are also a good bridging donors for
the construction of polymetallic species. Here we describe
the coordination chemistry of 2,7-bis(2-pyridinyl)-9-phen-
ylanthyridine toward ruthenium ions and the catalytic ac-
tivity of the resulting complexes on cyanation of tertiary
amine compounds.
Scheme II Preparation of the anthyridine ligand 4
Complexation of 4 with [RuCl2(CO)3(THF)] and
[(h6-p-cymene)RuCl2]2 was investigated (Shceme III). Re-
action of 4 with [RuCl2(CO)3(THF)] in a molar ratio of 1:2
provided the mono-nuclear complex 5 in 80% yield. We did
not observe the formation of dinuclear species in this reac-
tion, even with excess of ruthenium precursor or at a higher
reaction temperature. On the other hand, treatment of 4
with equal molar amount of [(h6-p-cymene)RuCl2]2 yielded
a di-ruthenium complex 6 in 89% yield.
Naphthyridine and anthyridine-based lig-
ands
Scheme I
Both complexes 5 and 6×(CH2Cl2)2 were isolated as
crystalline solids and were thoroughly characterized by
NMR spectroscopic and x-ray crystallographic analyses.
The presence of CO bands (2126, 2086, and 2068 cm-1) in
the IR spectrum of 5 are quite similar to those of
[{(bpy)Ru(CO)3Cl}{Ru(CO)3Cl3}], suggesting that
RESULTS AND DISCUSSION
Preparation and Characterization of Complexes
Ligand 4 was prepared by a double Friedländer reac-
tion according to the literature procedure (Scheme II).6
Starting with 1, aminolysis followed by the conversion of
the cyano group into the carbaldehyde gave 2,6-diamino-
Special Issue Dedicated to Prof. Yu Wang in Honor of Her 70th Birthday
* Corresponding author. E-mail: stliu@ntu.edu.tw
J. Chin. Chem. Soc. 2013, 60, 839-845
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Lo et al.
Table 1. Selected 1H NMR shifts of anthyridine ligand in
Coordination of 4 with ruthenium com-
plexes
Scheme III
complexes 5 and 6
Ph
b
c
d
a
N
N
N
N
N
Complex
5
6
H-a
H-b
H-c
H-d
8.85 (m)a
9.02 (d)
8.78 (m)a
8.36 (d)
8.77 (d)
8.85 (d)
8.85 (d)
8.77 (d)
[a] Overlapped with other protons
RuCl2(CO)3(THF) undergoes not only the coordination to-
ward ligand 4 also the disproportion reaction to yield the
anion of [Ru(CO)3Cl3]. 13C NMR spectrum of 5 shows four
peaks for the carbonyl carbon atoms. Accordingly, the CO
carbon atoms of the anion part [Ru(CO)3Cl3]- is chemically
equivalent and appear at d 185.3 as a single shift. Three
other CO-carbon signals are assigned to the CO-carbon of
“Ru(CO)3Cl” coordinating to the ligand. The carbonyl car-
bon atoms in trans position of the ligand and chloride are
chemically non-equivalent; each CO ligand has its own res-
onance and three carbonyl carbon shifts are observed at d
187.7, 184.7 and 182.8 ppm.
1H NMR shifts of the anthyridine ligand in the com-
plex 5 also provide useful structural information. These
chemical shifts are summarized in Table 1. In contrast to
the free ligand, the 1H NMR spectrum of 5 exhibits 10 sig-
nals for the anthyridinyl and pyridinyl groups (resonances
of three protons are overlapped), which clearly indicates
the unsymmetric nature of the complex.
arene (centroid) bond axis.7 In addition to the spectro-
scopic analysis, the detailed coordination configurations of
complexes 5 and 6×(CH2Cl2)2 were confirmed by X-ray dif-
fraction analysis on their single crystals.
Crystallography
Both complexes 5 and 6×(CH2Cl2)2 were obtained in
single crystalline form by re-crystallization from dichloro-
methane/hexane solutions. The crystal structure of 6 has
been solved and refined, despite the crystal exhibiting as a
twin crystal with disorder phenomena. The ORTEP plots of
5 and 6 are depicted in Figures 2 and 3, respectively. Se-
lected bond distances and bond angles are collected in Ta-
bles 2 and 3, respectively.
The molecular structure of 5 displays an octahedral
geometry with a chelating bound anthyridine, a chloride
and three carbonyl ligands completing the coordination
sphere at the metal center. The bipyridine fragment of 4 and
the chloride ligand around the metal center in complex 5
are arranged in a facial configuration due to the trans-influ-
For complex 6, the 1H NMR spectrum reveals that the
anthyridine protons of the ligand 4 are split into two set of
doublets (Table 1). In addition, four sets of resonances cor-
1
responding to the pyridinyl protons of 6 appear in its H
NMR spectrum. These observations clearly suggest the
symmetrical nature of the complex, which is consistent
with the proposed structure. However, the signals for the
p-cymene ring protons show to be broad at 298 K (Figure
1a). By lowering the temperature, the splitting pattern of
these protons becomes clear and appears to two sets of dou-
blet as expected (Figure 1d). This observation is in agree-
ment with other related h6-p-cymene ruthenium com-
plexes, which is due to the different conformers obtained
by the rotation of the p-cymene ring about the ruthenium-
Fig. 1. NMR spectra of p-cymene ring protons in 6.
840
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CHEMICAL SOCIETY
Cyanation of Arylamines
Table 2. Selected bond distances (Å) and bond angles (deg) for 5
ence. This coordination mode is very similar to that of
[{(bpy)Ru(CO)3Cl}{Ru(CO)3Cl3}].8 The ligands around
the ruthenium center of the anion part are also seated in the
facial arrangement. The angle P(1)-Ru(1)-N(1) [77.21(9)o]
is not 90o, showing a small bite angle attributable to the bi-
pyridine fragment. The bond lengths Ru(1)-N(1), Ru(1)-
N(2) and Ru(1)-Cl(1) are 2.102(2), 2.112(2) and 2.3831(8)
Å, respectively. These compare well to those observed in
related Ru(II) complexes.8
Ru(1)-Cl(1)
Ru(1)-C(2)
Ru(1)-N(1)
C(1)-O(1)
C(3)-O(3)
2.3831(8) Ru(1)-C(1)
1.910(4)
1.914(4)
2.112(2)
1.119(4)
1.882(4)
1.947(3)
2.102(2)
1.089(4)
1.125(4)
77.21(9)
Ru(1)-C(3)
Ru(1)-N(2)
C(2)-O(2)
Ru(2)-C(31)
N(1)-Ru(1)-C(2) 174.24(11)
N(1)-Ru(1)-N(2)
N(2)-Ru(1)-C(3)
171.41(12) Cl(1)-Ru(1)-C(1) 178.40(10)
Cl(2)-Ru(2)-C(31) 177.68(11) Cl(2)-Ru(2)-C(32) 86.87(11)
As shown in Fig. 3, complex 6 consists of two [(p-cy-
mene)RuCl] groups linked by the anthyridine ligand 4
through the chelation of two bipyridine fragments. Both ru-
thenium atoms in 6 are surrounded by the h6-bonded p-cy-
mene ring, a chelating bipyridine fragment, and the chlo-
ride and attains a pseudo octahedral “three legged piano
stool” geometry.7 A notable feature of the structure 6 is that
two cymene rings are opposite along the anthyridine rings
presumably due to the steric interaction. All Ru-N bond
lengths are quite similar, at 2.06 ~ 2.12 Å, which are in
agreement with those of other reported ruthenium p-cy-
mene complexes.7 Both bite angles N(1)-Ru(1)-N(2)
[77.7(3)o] and N(4)-Ru(2)-N(5) [77.1(3)o] are similar to
that of 5 and comparable to those of [(bipyridine)RuCl(L)].
Table 3. Selected bond distances (Å) and bond angles (deg) for 6
Ru(1)-N(1)
Ru(1)-N(2)
Ru(1)-Cl(2)
2.068(6)
2.111(7)
2.387(2)
Ru(2)-N(4)
Ru(2)-N(5)
Ru(2)-Cl(1)
N(4)-Ru(2)-N(5)
2.119(7)
2.062(6)
2.375(2)
77.1(3)
N(1)-Ru(1)-N(2) 77.7(3)
N(1)-Ru(1)-Cl(2) 81.75(18) N(4)-Ru(2)-Cl(1) 86.49(18)
N(2)-Ru(1)-Cl(2) 88.05(17) N(5)-Ru(2)-Cl(1) 82.31(18)
of these species particularly the di-ruthenium complex 6. In
recent works, Murahashi and co-workers have successfully
demonstrated the use of ruthenium complexes on the oxi-
dative cyanation of tertiary amines with NaCN.9 Few other
reports concerning this catalysis also appeared.10 Here, we
investigate the catalytic activity of complexes 5 and 6 on
the oxidative a-cyanation of tertiary amines.
...
The distance of Ru(1) Ru(2) is 5.443 Å, indicating that
two metal centers are far away from each other.
Catalysis
To obtain information on the catalytic systems, we
explored the a-cyanation of N,N-dimethylaniline with
NaCN as a model system (Eq. 1). In a typical experiment
for the reaction, a mixture of N,N-dimethylaniline, NaCN
and Ru(II) complex (mole ratio = 1: 1.2 : 0.01) in a solution
According to the above investigation on Ru(II) com-
plexes, it would be interesting to test the catalytic activity
Fig. 3. ORTEP plot of 6 (Drawn with 30% probability
Fig. 2. ORTEP plot of 5 (Drawn with 30% probability
ellipsoids).
ellipsoids).
J. Chin. Chem. Soc. 2013, 60, 839-845
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Table 4. Results of a-cyanation of C6H5N(CH3)2 with NaCNa
Entry Catalyst Oxidant Solventb Temp. Time(h) Yieldc
(selected solvent/acetic acid = 3:1, 0.4 mL) was heated to
60 oC in the presence of oxidant for a certain period. The
desired product 7 was extracted and then analyzed by 1H
NMR spectroscopy. Results are summarized in Table 4.
1
2
3
4
5
6
7
8
5
O2
O2
O2
O2
-
O2
O2
O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
MeOH
MeOH
MeOH
MeOH
MeOH
60 oC
60 oC
60 oC
60 oC
60 oC
24 h
2 h < 10%
0%
6
6d
2 h
24 h
24 h
24 h
24 h
24 h
24 h
24 h
24 h
24 h
8 h
20%
37%
0%
68%
67%
6%
28%
100%
0%
28%
100%
16%
38%
6
6
6
Me2CHOH 80 oC
i-AmOH 100 oC
toluene 100 oC
6
6
e
e
e
e
f
9e
10
11e
12
13
14
15
6
MeOH
MeOH
MeOH
CH3CN
MeOH
MeOH
MeOH
25 oC
60 oC
60 oC
60 oC
60 oC
60 oC
60 oC
From entries 1~2 and 13~15 (Table 4), these results
clearly reveal that the di-ruthenium complex 6 is the best
catalyst for this transformation, whereas the mono-nuclear
complexes show less activity. This catalytic conversion
was also influenced by the oxidants. The yield of cyanation
product could not reach to 100% by using dioxygen as the
oxidant. By using excess amount of hydrogen peroxide as
the oxidant increases the conversion dramatically (Table 4,
entry 6). Notably, by a slow addition of H2O2 to the reaction
mixture, the amount of reagent could be reduced (Table 4,
entry 13). Among the solvents tested, methanol gave the
cyanation product 7 in the highest yield.
6
6
6
6
f
f
5 g
8 g
24 h
24 h
a N,N-dimethylaniline (0.25 mmol), Ru(II) complex (1 mol%),
NaCN (0.3 mmol) in a solution. b A mixed solvent (organic
solvent/acetic acid: 0.3 mL/0.1 mL). c NMR yields. d 5 mol%.
e 0.6 mmol. e No acetic acid. f 0.25 mmol, but was added
gradually over 40 min. g 2 mol%.
Ph2
P
Ru(CO)2Cl
N
O
To further validate the activity of the complex 6, a se-
ries of arylamines were also subjected to the in situ oxida-
tion-imine formation conditions (Table 5). Under the opti-
mal catalytic conditions, various para-substituted dimeth-
yl-anilines provided the corresponding cyanation product
quantitatively, except the amino-substituted one (Table 5,
entry 6). For diethylarylamine, the cyanation took place at
a-position, as expected, to give N-ethyl-N-(1-cyanoethyl)-
aniline in 73% yield. However, we did not obtain any di-
cyanation product even with the prolong heating or excess
of reagents. For the selectivity, the cyanation prefers to take
place at the methyl group over the ethyl as illustrated in en-
try 8. Thus, the catalytic reaction of N-ethyl-N-methyl-
aniline with NaCN yielded N-ethyl-N-(cyanomethyl)ani-
line as the exclusive product.
8
currently in progress.
EXPERIMENTAL
General information. All reactions and manipulations
steps were performed under a nitrogen atmosphere. Dichloro-
methane and acetonitrile were dried over CaH2 and distilled under
nitrogen. Other chemicals and solvents were of analytical grade
and were used after degassed process. Nuclear magnetic reso-
nance spectra were recorded on a Bruker AVANCE 400 spectrom-
eter. Chemical shifts are given in parts per million relative to
Me4Si for 1H and 13C NMR. Infrared spectra were measured on a
Nicolet Magna-IR 550 spectrometer (Series-II). UV-Vis spectra
were recorded on a Hitachi U-2900 spectrometer. Compound 3
was prepared according to the reported method.6
CONCLUSIONS
In summary, we have prepared and characterized ru-
thenium complexes containing a 2,7-dipyridinylanthyri-
dine ligand. Further utilization of these complexes for a-
cyanation of tertiary arylamines with NaCN was investi-
gated. It appears that di-ruthenium complex 6 is an excel-
lent catalyst for the a-cyanation of N,N-dialkylanilines,
presumably due to the cooperative effect between the two
ruthenium centers in the complex. Further studies concern-
ing the cooperative effect between metal centers in 6 are
Ligand 4. A mixture of di-aldehyde 3 (0.10 g, 0.42 mmol)
and 2-acetylpyridine (0.1 g, 0.85 mmol) in ethanol (4 mL) was
heated at 60 oC for 2 h. A solution of 10% KOH in ethanol (0.1
mL) was added to the above reaction mixture. The resulting mix-
ture was heated to reflux for another 12 h. After cooling, the mix-
ture was extracted with CH2Cl2/water and the organic extracts
were concentrated to give yellow brown solids. The crude product
842
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Cyanation of Arylamines
Table 5. a-Cyanation of various tertiary aminesa
NMR (100 MHz): d 187.7, 185.3, 184.7, 182.8, 164.5, 162.2,
156.7, 155.5, 155.0, 154.8, 154.2, 150.7, 149.6, 144.0, 142.8,
137.4, 137.2, 132.0, 130.7, 130.5, 129.5, 129.3, 126.0, 123.4,
122.7, 121.9, 121.5; ESI-MS: m/z calcd. for 604.01
C29H17ClN5O2Ru ([M-Ru(CO)3Cl3-CO]+), found 604.08; IR
(KBr): 2126, 2057, 1995 cm-1 (uCO); UV-Vis (acetone): lmax
(e[M-1cm-1]) = 331 (10000), 410 (29000).
Entry
Substrate
Time
Product (yield)
CH3
CH3
C6H5
N
C6H5
N
1
8 h
CN (100%)
CH3
CH3
CH3
p-Me-C6H4
N
p-Me-C6H4 N
2
3
4
5
6
10 h
10 h
8 h
CH3
CH3
CN
(100%)
Complex 6. A mixture of 4 (60 mg, 0.15 mmol), [(h6-p-cy-
mene)RuCl2]2 (95 mg, 0.16 mmol) and KPF6 (45 mg, 0.24 mmol)
in a round-bottom flask was flashed with nitrogen and then added
acetonitrile (5 mL). The resulting mixture was heated to reflux for
12 h. After removal of solvent, the residue was washed with
CH2Cl2, methanol and water. Complex 4 was obtained (146 mg,
89%). Recrystallization from CH2Cl2 at -20 oC gave 6 as golden
yellow crystalline solids suitable for X-ray structural analysis. 1H
NMR (400 MHz, d6-acetone, at 223 K): d 9.74 (d, J = 7 Hz, 2H,
Py-H), 9.15 (d, J = 7 Hz, 2H, Py-H), 8.85 (d, J = 7 Hz, 2H, An-H),
8.77 (d, J = 7 Hz, 2H, An-H), 8.56 (t, J = 7 Hz, 2H, Py-H), 8.12 (t,
J = 7 Hz, 2H, Py-H), 7.93 (m, 3H, Ph-H), 7.76 (m, 2H, Ph-H), 7.35
(d, J = 7 Hz, 2H, Ar-H), 6.51 (br, 4H, Ar-H), 6.23 (d, J = 7 Hz, 2H,
Ar-H), 3.21 (m, 1 H, -CH), 2.61 (s, 3H,-CH3), 1.61 (br, 6H, -CH3),
1.42 (m, 1 H, -CH), 0.93 (s, 3 H, -CH3), 0.50 (m, 3H, -CH3), 0.25
(br, 3H, -CH3). 13C NMR (100 MHz, d3-CD3CN): d 165.3, 158.5,
157.5, 157.2, 155.4, 142.2, 141.2, 133.3, 132.3, 131.8, 130.6,
130.4, 128.5, 124.1, 121.9, 107.5, 102.6, 88.3, 86.0, 84.9, 31.9,
22.5, 21.5, 18.6; ESI-MS: m/z calcd. for 1098.08 [C47H45Cl2F6N5PRu2
([M-Cl]+)], found 1098.17; UV-Vis (acetone): lmax (e[M-1cm-1])
= 337 (19000), 377 (22000), 396 (26000), 417 (28000), 512
(5100).
CH3
p-Br-C6H
4 N
p-Br-C6H4
N
CN
CH3
(100%)
CH3
CH3
p-F-C6H4
N
p-F-C6H4
m-BrC6H4
N
N
CN
CH3
CH3
(100%)
CH3
m-BrC6 H4N
24 h
24 h
CH3
CH3
CN
(100%)
p-H2NC6 H4
N
No reaction
CH3
CH2CH3
CH2CH3
C6H5
N
C6H5
N
7
24 h
CHCH3
CN
CH2CH3
CH2CH3
(73%)
CH2CH3
C6H5
N
C6H5
N
8
24 h
CH2CN
CH3
(100%)
a Amine (0.25 mmol), complex 6, and NaCN (0.3 mmol) in a
solution of MeOH/acetic acid: 0.3 mL/0.1 mL was heated at 60
oC with a slow addition of H2O2 (0.25 mmol).
was crystallized from CH2Cl2/hexane to give 4 as yellow solids
(0.13 g, 73%): 1H NMR (400 MHz, CDCl3): d 9.07 (d, J = 8.0 Hz,
2H, Py-H), 8.75 (d, J = 8.0 Hz, 2H, An-H), 8.68 (d, J = 8.0 Hz, 2H,
Py-H), 8.23 (d, J = 8.0 Hz, 2H, An-H), 7.92 (t, J = 8.0 Hz, 2H,
Py-H), 7.65 (m, 3H, Ph-H), 7.49 (m, 2H, Ph-H), 7.40 (m, 2H,
Py-H). 13C NMR (100 MHz): d 161.8, 156.0, 155.2, 151.0, 149.1,
137.1, 136.6, 134.1, 130.7, 129.2, 128.9, 125.1, 123.3, 120.6,
119.7.
General Procedure for Catalysis. A mixture of amine
(0.25 mmol), complex 6, and NaCN (0.3 mmol) in a solution of
o
MeOH/acetic acid: 0.3 mL/0.1 mL) was heated at 60 C. H2O2
(0.25 mmol) was added slowly (over a period of 40 min). The
mixture was stirred at 60 oC for a certain period. After the reac-
tion, water and ethyl acetate were added. The organic extract was
separated, dried and concentrated. The desired product was puri-
fied by chromatography with CH2Cl2/EtOAc as eluent. All prod-
ucts were characterized by 1H and 13C NMR spectroscopy.
Spectroscopic Data for the Cyanation Products
N-(Cyanomethyl)-N-methylaniline. 1H NMR (400 MHz,
CDCl3): d 3.00 (s, 3 H, -CH3), 4.17 (s, 2 H, -CH2), 6.90 (br, 3 H,
Ar-H), 7.30 (t, J = 6 Hz, 2 H, Ar-H). 13C NMR (100 MHz, CDCl3):
d 147.6, 129.3, 120.1, 115.3, 114.8, 42.4, 39.3. N-(Cyanometh-
yl)-N-methyl-p-methylaniline. 1H NMR (400 MHz, CDCl3): d
2.28 (s, 3 H, -CH3), 2.95 (s, 3 H, -CH3), 4.11 (s, 2H, -CH2), 6.79
(d, J = 8 Hz, 2 H, Ar-H), 7.11 (d, J = 8 Hz, 2 H, Ar-H). 13C NMR
Complex 5. A mixture of 4 and [RuCl2(CO)3(THF)] (80
mg, 0.25 mmol) in CHCl3 (5 mL) was heated at 40 oC for 12 h. Af-
ter removal of solvents, the residue was re-precipitated in CH2Cl2/
hexane. The desired complex 5 was obtained as brownish solids
after filtration (89 mg, 80%). 1H NMR (400 MHz, CDCl3): d 9.31
(d, J = 8 Hz, 1H, Py-H), 9.13 (d, J = 8 Hz, 1H, Py-H), 9.02 (d, J = 8
Hz, 1H), 8.91 (d, J = 8 Hz, 1H, An-H), 8.89 (d, J = 8 Hz, 1H,
An-H), 8.80 (d, J = 8 Hz, 1H, An-H), 8.85 (m, 1H, Py-H), 8.61 (t,
J = 8 Hz, 1H, Py-H), 8.36 (d, J = 8 Hz, 1H, An-H), 7.96 (t, J = 8
Hz, 1H, Py-H), 7.87 (t, J = 8 Hz, 1H, Py-H),7.70 (m, 3H, Ph-H),
7.60 (m, 1H, Ph-H), 7.49 (m, 1H, Ph-H), 7.40(m, 1H, Py-H). 13
C
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Lo et al.
Table 6. Crystal data for 5 and 6.(CH2Cl2)2
2 H, Ar-H). 13C NMR (100 MHz): d 146.5, 129.3, 121.7, 119.5,
116.2, 114.6, 46.2, 39.4, 12.2.
Complex
5
6.(CH2Cl2)2
Crystallography. Crystals suitable for X-ray determina-
tion were obtained for 5 and 6×(CH2Cl2)2 by recrystallization at
room temperature. Cell parameters were determined either by a
Siemens SMART CCD diffractometer. The structure was solved
using the SHELXS-97 program11a and refined using the
SHELXL-97 program11b by full-matrix least-squares on F2. It
should be noted that 6 were in twin crystals and refined SHELXL
HKLF 5 (two sets) programs. CCDC-921735 (5) & 921736 (6)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
Formula
Fw
Crystal system
Space group
a, Å
b, Å
c, Å
a, deg
b, deg
C33H17Cl4N5O6Ru2
923.46
Monoclinic
P2(1)/n
11.0852(3) Å
21.4350(5) Å
14.6507(4) Å
90
95.887(3)
90
C48H47Cl4F12N5P2Ru2
1327.79
Monoclinic
P2(1)/n
19.168(2)
11.0351(5)
27.4941(14)
90
105.048(8)°
90
5616.3(7), 4
1.570
2656
0.15 ´ 0.10 ´ 0.10
16711
g, deg
V, Å3; Z
3462.81(16), 4
d (calc.), Mg/m3 1.771
F(0,0,0)
1816
Crystal size, mm3 0.20 ´ 0.15 ´ 0.10
Rflns collected 24984
16716 [R(int) =
0.0000]
Independent rflns 7941 [R(int) = 0.0357]
ACKNOWLEDGEMENTS
q range, deg
2.91 to 27.50°
2.98 to 27.50°
We thank the National Science Council for financial
support (NSC-100-2113-M002-001-MY3).
Refined method Full-matrix least-squares on F2
Goodness of fit
1.031
1.376
on F2
R indices [I >
2s(I)]
R indices (all
data)
R1 = 0.0354, wR2 =
0.0634
R1 = 0.0616, wR2 =
0.0721
R1 = 0.0794, wR2 =
0.2027
R1 = 0.1201, wR2 =
0.2199
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(100 MHz): d 145.6, 129.9, 129.8, 115.4, 115.3, 42.7, 39.4, 20.3.
1
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