Synthesis of Homoleptic and Heteroleptic Ruthenium Complexes Appended with Glucosyl Ligand by the Click-to-Chelate Approach

Article abstract of DOI:10.1134/S1070363217120507

Homoleptic and heteroleptic complexes of Ru(TAGP-tapy)₃Cl₂ {TAGP-tapy is 2-[1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-1H-1,2,3-triazol-4-yl]-pyridine} bearing a clustered glucose-derived ligand and Ru(bpy)₂(TAGP-tapy)Cl₂ (bpy is 2,2'-bipyridine) have been synthesized by the chelating reaction of RuCl₃·3H₂O with TAGP-tapy and cis-Ru(bpy)₂Cl₂ with TAGP-tapy, respectively. The bidentate 1,2,3-triazolelinked glucose-derived ligand TAGP-tapy was prepared by copper-catalyzed coupling (click reaction) of 2-ethynylpyridine with acetyl protected glucosyl azide, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl azide (TAGP-N₃). TAGP-N₃ was prepared by nucleophilic substitution reaction of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (TAGP-Br) with NaN₃. These ruthenium complexes were purified by column chromatography or HPLC. Structures of the intermediates and ruthenium complexes were confirmed by HPLC, ¹H and ¹³C NMR, FT-IR, and ESI-MS spectroscopies. UV-Vis and fluorescence spectroscopic methods were used to study optical properties of the ligand TAGP-tapy and ruthenium complexes. TAGP-tapy exhibited interesting solvent-polarity dependent fluorescence properties and a significant red-shift in emissions. Both complexes demonstrated distinctive fluorescence emission band in the visible region.

Full text of DOI:10.1134/S1070363217120507

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 12, pp. 3036–3042. © Pleiades Publishing, Ltd., 2017.
Synthesis of Homoleptic and Heteroleptic Ruthenium Complexes
Appended with Glucosyl Ligand
by the Click-to-Chelate Approach1
N. Xiao*, A. Cheng, Q. G. Zhu, Q. Cheng, R. B. Wu, B. R. Yu, and Z. Wang
School of Pharmaceutical Sciences, Capital Medical University, Beijing, 100069 China
*e-mail: xiaonao@ccmu.edu.cn
Received October 9, 2017
Abstract―Homoleptic and heteroleptic complexes of Ru(TAGP-tapy)3Cl2 {TAGP-tapy is 2-[1-(2,3,4,6-tetra-
O-acetyl-β-D-glucopyranosyl)-1H-1,2,3-triazol-4-yl]-pyridine} bearing a clustered glucose-derived ligand and
Ru(bpy)2(TAGP-tapy)Cl2 (bpy is 2,2'-bipyridine) have been synthesized by the chelating reaction of
RuCl3·3H2O with TAGP-tapy and cis-Ru(bpy)2Cl2 with TAGP-tapy, respectively. The bidentate 1,2,3-triazole-
linked glucose-derived ligand TAGP-tapy was prepared by copper-catalyzed coupling (click reaction) of
2-ethynylpyridine with acetyl protected glucosyl azide, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl azide
(TAGP-N3). TAGP-N3 was prepared by nucleophilic substitution reaction of 2,3,4,6-tetra-O-acetyl-α-D-
glucopyranosyl bromide (TAGP-Br) with NaN3. These ruthenium complexes were purified by column
chromatography or HPLC. Structures of the intermediates and ruthenium complexes were confirmed by HPLC,
1H and 13C NMR, FT-IR, and ESI-MS spectroscopies. UV-Vis and fluorescence spectroscopic methods were
used to study optical properties of the ligand TAGP-tapy and ruthenium complexes. TAGP-tapy exhibited
interesting solvent-polarity dependent fluorescence properties and a significant red-shift in emissions. Both
complexes demonstrated distinctive fluorescence emission band in the visible region.
Keywords: homoleptic ruthenium complex, heteroleptic ruthenium complex, glucosyl ligand, click-to-chelate,
carbohydrate-protein interactions
DOI: 10.1134/S1070363217120507
INTRODUCTION
carbohydrate-functionalized fluorescent markers over
recent years. A carbohydrate clustered around the
metal center would enhance the binding constant of
generally weak interaction among carbohydrates and
proteins. A metalloglycocluster is an especially
attractive carbohydrate probe, since the metal center
determines characteristic photochemical and electro-
chemical properties that can be utilized as an indicator.
Based on the above, this study targeted synthesis of the
fluorescent-labeled carbohydrate as a probe molecule.
Carbohydrate-protein interactions mediate many
important physiological processes, such as cell growth,
interactions with bacteria and viruses, and functioning
of immune system, that are important for drug
development and clinical diagnostics [1, 2]. Since
proteins responsible for cellular recognition processes
are found in aggregates that present multiple binding
sites for mono-valent carbohydrate interaction, this
natural multivalency enhances the binding affinity of
mono-valent carbohydrate-protein interaction, which is
known as cluster glycoside effect [3]. Dendritic poly-
mers and organic compounds modified with carbo-
hydrates at their branches by the click reaction were
reported recently [4, 5]. Chemical labeling of non-
ultraviolet or non-fluorescent carbohydrates with the
fluorescent tag is an essential step that makes the intra-
cellular microscopic insight possible [6]. Therefore,
there has been a growing interest in developing
Many efforts have already been directed towards
design and synthesis of various sugar containing struc-
tures based on the metal-ligand non-covalent inter-
actions. A big number of sugars ruthenium complexes
with various topologies, such as linear, star and
dendritic, have been synthesized [7]. In general, bi-
pyridine, phenanthroline and diketone derivatives are
used as ligands chelating with ruthenium ion to form
certain structures [8–13]. The copper catalyzed click
reaction of azides with alkynes containing amino
groups, such as 2-ethynylprydine, has been developed
1 The text was submitted by the authors in English.
3036

SYNTHESIS OF HOMOLEPTIC AND HETEROLEPTIC RUTHENIUM COMPLEXES
3037
Scheme 1. Synthesis of TAGP-tapy, Ru(bpy)2(TAGP-tapy)Cl2, and Ru(TAGP-tapy)3Cl2.
OAc
OAc
NaN3
DMF
O
O
AcO
AcO
AcO
AcO
N3
AcO
AcO
Br
TAGP-Br
TAGP-N3
OAc
N
O
CuSO4 5H2O, Ascorbic acid
DMF
AcO
N
N
AcO
N
N
AcO
TAGP-tapy
OAc
N
2+
OAc
O
RuCl3 3H2O
DMF
Ru
AcO
AcO
N
N
2Cl−
N
N
O
N
AcO
AcO
AcO
N N
AcO
3
TAGP-tapy
Ru(TAGP-tapy)3Cl2
N
N
N
2+
Ru
cis-Ru(bpy)2Cl2
OAc
O
CH2Cl2 : MeOH
N
2Cl−
AcO
N N
AcO
2
AcO
Ru(bpy)(TAGP-tapy)2Cl2
as one of the promising methods for preparing
bidentate amine ligands consisting of the 1H-1,2,3-
triazole (tapy) group. Synthesis of metal complexes
using a multidentate chelating ligand with 1H-1,2,3-
triazole ring is called click-to-chelate. Earlier we have
reported a one-pot synthesis of 3- to 12-arm star
branched polymer Ru(II) complexes and stepwise
chelating synthesis of copolymers by the click-to-
chelate approach [14–17]. In the current study we
designed homoleptic and heteroleptic ruthenium com-
plexes, Ru(TAGP-tapy)3Cl2 and Ru(bpy)2(TAGP-tapy)Cl2,
appended with different glucosyl ligands as potential
carbohydrate probes (Scheme 1).
TAGP-N3 was synthesized by nucleophilic substa-
tion of TAGP-Br with NaN3. The following synthesis
of the ligand TAGP-tapy involved the click process of
TAGP-N3 with 2-ethynylpyridine. Then the homoleptic
and heteroleptic ruthenium complexes were designed.
Arms of the ruthenium complexes were held together
by a luminescent Ru(II) core, appended with glucosyl
ligand by the click-to-chelate approach. Two types of
ruthenium complexes containing different cores and
ligands were synthesized aiming systematic study of
effects of the core linkage and their composition
influence on the carbohydrate-protein binding. In
general, preparation of the homoleptic and heteroleptic
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3038
XIAO et al.
Wavelength, nm
Fig. 2. UV-Vis absorption and fluorescence spectra of
TAGP-tapy: (1) THF, (2) DMF–H2O = 3 : 5, and (3)
MeCN–H2O = 3 : 7. The emission spectrum was
obtained after excitation at 280 nm for TAGP-tapy,
λex = 280 nm.
δ, ppm
1
Fig. 1. H NMR spectra of TAGP-N3 and TAGP-tapy in
CDCl3.
ruthenium complexes can be implemented via two
strategies (Scheme 1):
group completely disappeared upon completion of the
click reaction with 2-ethynylpyridine. In the H NMR
1
spectrum of TAGP-N3 (Fig. 1), the signals of
neighboring the azido group proton (f') and methyne
protons on the pyraniod ring (g'–i', k') residue were
recorded at 3.82 ppm and in the range of 4.59–
5.31 ppm, respectively. The click reaction was also
(1) One pot complexation of Ru(TAGP-tapy)3]Cl2
using Ru(III)Cl3·3H2O with ligand TAGP-tapy.
(2) One pot complexation of Ru(bpy)2(TAGP-tapy)
Cl2 using cis-Ru(bpy)2Cl2 with ligand TAGP-tapy.
1
1
verified by H NMR measurements. In the H NMR
spectrum of TAGP-tapy (Fig. 1) the signals of protons
of the triazole cycle were observed at ca 8.43 ppm. In
ESI-MS spectrum of TAGP-tapy the main peak at
476.91 (m/z) was in good agreement with the formula
(C21H25N4O9, 477.16). According to the spectral data,
TAGP-N3 could be synthesized by the substitution
reaction, and TAGP-tapy could be quantitatively
synthesized via the click reaction.
The structures and properties of the synthesized
intermediates and non-covalent ruthenium complexes
1
were studied by means of FT-IR, H and 13C NMR,
ESI-MS, UV-Vis, and fluorescence spectroscopies. The
complexes synthesized in this study are expected to
provide more species of the sugar fluorescent markers
as probe molecules for investigating carbohydrate-
protein interactions.
RESULTS AND DISCUSSION
By coincidence, we detected fluorescence for the
solution of triazoyl-substituted TAGP in THF.
Photophysical study of TAGP-tapy demonstrated two
absorption bands with the maximum at ca 280 nm in
the UV-Vis spectrum (Fig. 2) and a fluorescence
emission maximum at 317 nm when excited at
280 nm. These results indicated that the fluorescence
properties were exclusively originated from the
conjugated triazole–pridine system. TAGP-tapy also
displayed positive solvatofluorochromism, the
fluorescence efficiency was increased with the increase
of solvent-polarity (Fig. 2). A red-shift of about 50 nm
was observed for the emission of TAGP-tapy from
317 nm in THF to 366 nm in a mixture of acetonitrile–
water. Such effect can lead to detection of triazole-
pyridine conjugated biologically active compounds by
the fluorescence method.
Synthesis of ligand TAGP-tapy. Acetyl protected
TAGP-Br was treated with sodium azide in dry DMF
to give TAGP-N3. The following cycloaddition reac-
tion of TAGP-N3 with an excess of 2-ethynylpyridine
was catalyzed by Cu(II) (Scheme 1). Upon conversion
of azide into the triazole substituted adduct TAGP-
tapy, the solvent was evaporated. TAGP-tapy was
obtained as the sole product with nearly quantitative
yield, although it was contaminated by copper ion. The
latter was removed by washing with ethyl acetate and
ammonia solution containing a small amount of EDTA
[20].
In the FT-IR spectrum introduction of the azido
group was recorded by presence of the characteristic
stretching band at ca 2100 cm–1. Bands of the azido
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SYNTHESIS OF HOMOLEPTIC AND HETEROLEPTIC RUTHENIUM COMPLEXES
3039
Wavelength, nm
Wavelength, nm
Fig. 3. UV-Vis absorption spectra of (1) TAGP-tapy,
(2) Ru(bpy)2(TAGP-tapy)Cl2, and (3) Ru(TAGP-tapy)3Cl2
in MeCN.
Fig. 4. Fluorescence spectra of (1) Ru(bpy)2(TAGP-tapy)Cl2
and (2) Ru(TAGP-tapy)3Cl2 in MeOH (λex = 370 nm).
Synthesis of homoleptic and heteroleptic ruthenium
complexes. As presented in Scheme 1, the glucosyl
possessing bidentate amine ligand TAGP-tapy reacted
with the precursor cis-Ru(bpy)2Cl2 in CH2Cl2 : MeOH
(1 : 1) under reflux to produce a stable heteroleptic
complex Ru(bpy)2(TAGP-tapy)Cl2. cis-Ru(bpy)2Cl2
gave a stable complex with the ligand with the ratio of
1 : 1. Ru(TAGP-tapy)3Cl2 was synthesized in one step
by the reaction of the ligand TAGP-tapy with RuCl3·
3H2O. The method is suitable for the synthesis of
homoleptic ruthenium complexes. Notably, RuCl3
trihydrate led to formation of homoleptic ruthenium
complexes more efficiently than anhydrous RuCl3,
because of poor solubility of the latter in most of
solvents. Both one-pot methods are very simple, rapid
and efficient for preparing heteroleptic and homoleptic
ruthenium complexes. Ruthenium complexes were
purified by column chromatography on silica with
MeCN : H2O : KNO3 (100 : 7.5 : 0.5) as an eluent.
Presence of some traces recorded by HPLC suggested
formation of Ru(bpy)2(TAGP-tapy)Cl2.
reported [17]. As a typical control spectrum, TAGP-
tapy exhibited the maximum absorbance at 280 nm due
to the electronic π–π* transition of the tapy moiety, and
a 285 nm band as a weak shoulder because of a π–π*
transition of one py ligand. Upon TAGP-tapy chelating
with RuCl3·3H2O and formation of Ru(TAGP-tapy)3]
Cl2, the above maximum absorbance had a blue shift to
267 nm, and the 285 nm absorption band was totally
absent in the spectrum due to lack of bpy ligand. A
new absorbance peak appeared at ca 371 nm due to the
metal-to-ligand charge transfer (MLCT) effect caused
by Ru(II)/tapy complex core. The characteristic maxi-
mum absorption band for Ru(TAGP-tapy)3Cl2 was
shifted to shorter wavelength than that of Ru(bpy)32+
complex (450 nm in acetonitrile) because of the poor
electro-accepting property of triazole ring. The MLCT
effect, on the other hand, resulted in the slightly yellow
color of the aq. Ru(TAGP-tapy)3]Cl2 solution. Ru(II)
Complexes of TAGP-tapy gave UV-Vis spectra similar
to those of [Ru(Bn-tapy)3](PF6)2, suggesting a similar
coordination on Ru(II) ions. The maximum absorbance
of Ru(bpy)2(TAGP-tapy)Cl2 (Fig. 3) presented a red
shift to 283 nm compared with TAGP-tapy, and a weak
shoulder was observed due to the presence of one tapy
moiety. The broad and relatively intense band at ca
430 nm was assigned to a metal-to-ligand charge-
transfer (MLCT) effect caused by the Ru(II)–(tapy and
bpy) complex core. The higher-energy shoulder
observed was assigned to the second MLCT transition.
Spectroscopic and photophysical studies demonstrate
that inherently favorable properties of the parent
complexes were not substantially altered by the ligand
substitutions.
The measured molecular-ion peaks appeared at
444.65 (calculated 444.10) for Ru(bpy)2(TAGP-tapy)2+
and 764.50 (calculated 765.185) for Ru(TAGP-tapy)32+.
Additionally, ESI-MS spectra of the complexes
indicated that the tapy moiety acted as a bipyridine-
1
like chelator. H NMR spectrum of Ru(bpy)2(TAGP-
tapy)Cl2 was complicated because of the overlap of
two ligands bands and a mixture of the fac- and mer-
isomers.
UV-Vis and fluorescence spectroscopies were used
to assess the optical properties of Ru(TAGP-tapy)3]Cl2
and Ru(bpy)2(TAGP-tapy)]Cl2. Absorption spectra of
the complexes were similar to those of PSO-sub-
stituted ligands and ruthenium complexes previously
Room-temperature fluorescence emission spectra of
the complexes recorded in MeOH (Fig. 4) demonstrated
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3040
XIAO et al.
maximum excitation wavelength at 450 nm for
Ru(bpy)2(TAGP-tapy)Cl2 and 370 nm for Ru(TAGP-
tapy)3Cl2. Electronic emission spectra of the com-
plexes exhibited strong bands at 590 nm for
Ru(bpy)2(TAGP-tapy)Cl2 and at 417 nm for Ru(TAGP-
tapy)3Cl2. Fluorescence properties studies of
Ru(bpy)2(TAGP-tapy)Cl2 and Ru(TAGP-tapy)3Cl2
indicated their potential in imaging proteins within
living cells.
1 : 2, Rf = 0.45). TAGP-tapy was obtained as a white
solid, Yield 89.0%. IR spectrum, ν, cm–1: 2120, 1748,
1372, 1245, 1209, 1064, 906. H NMR spectrum, δ,
ppm: 5.23 t (1H), 5.11 t (1H), 4.98 t (1H), 4.65 d (1H),
4.32–4.12 m (2H), 3.84–3.76 m (1H), 2.11–2.01 s.s.s.s
(12H). 13C NMR spectrum, δ, ppm: 170.58, 170.10,
179.25, 169.18, 87.91, 74.02, 72.61, 70.72, 67.90,
61.75, 20.65, 20.54, 20.51, 20.50.
1
Synthesis of 2-[1-(2,3,4,6-tetra-O-acetyl-β-D-gluco-
pyranosyl)-1H-1,2,3-triazol-4-yl]-pyridine (TAGP-tapy).
TAGP-tapy was prepared according to a literature
procedure [19]. A mixture of TAGP-N3 (186.7 mg,
0.5 mmol) with 2-ethynylpyridine (61.9 mg,
0.6 mmol), Cu(II) sulfate pentahydrate (25.0 mg,
0.1 mmol) and ascorbic acid (35.2 mg, 0.2 mmol) in
DMF (15 mL) were stirred at room temperature under
TLC monitoring (eluent: petroleum ether–ethyl acetate =
1 : 1, Rf = 0.4). The solvent was removed under
reduced pressure, the residue was diluted with H2O
(50 mL) and extracted with CH2Cl2 (3×50 mL). The
combined organic layers were washed with a bit of
EDTA in aqua ammonia (20 mL), dried above Na2SO4,
filtered, and concentrated. Flash chromatography with
PE/EtOAc as an eluent, gave TAGP-tapy as white
solid, 86.0%. IR spectrum, ν, cm–1: 2120, 1608, 1461,
EXPERIMENTAL
All chemicals and reagents were of analytical grade
or of the highest purity available and used without
further purification. Ultrapure water was used
throughout the experiments. Most of reagents and
solvents were purchased from Aladdin Reagent
(Shanghai, China). TLC analyses were performed on
silica gel plates and column chromatography was
carried out on silica gel (200–300 mesh), purchased
form Qingdao Haiyang Chemicals. A semi-preparative
column (Dikma Tech. Inc., Luster C18, 10 mm,
21.2×250 mm) was used to purify ruthenium com-
plexes. Purity of ruthenium complexes (>98%) and the
intermediates (>95%) were determined by TLC
(Qingdao silica gel plates of GF254, 0.25 mm layer
thickness) and HPLC analysis (Waters, C18 column,
4.6×150 mm). UV-Vis absorption spectra were
recorded on a SHIMADZU UV-2550 spectrophoto-
meter. Fluorescence was recorded on a HITACHIF-
2500 fluorescence spectrometer with the excitation and
emission slit widths at 5.0 nm. FT-IR spectra were
recorded on a Thermo Nicolet IS5, Thermo Fisher
Scientific, USA). 1H and 13C NMR spectra were
measured on a Varian INOVA-300 MHz spectrometer
with TMS as the internal standard. ESI/MS spectra
were measured on a ZQ 2000 (Waters, US) and solariX
FT-ICR mass spectrometer (Bruker Daltonik) with an
ESI/MALDI dual ion source and 9.4 T super-
conductive magnet.
1
1425, 1372, 1215, 1114, 1028. H NMR spectrum, δ,
ppm: 8.61 d (1H), 8.44 s (1H), 8.16 d (1H), 7.85–7.76
m (1H), 7.30–7.22 m (1H), 5.98–5.92 d (1H), 5.55–
5.46 m (2H), 5.27 t (1H), 4.37–4.28 m (1H), 4.20–4.13
m (1H), 4.09–4.01 m (1H), 2.10–1.90 s.s.s.s (12H). 13C
NMR, spectrum, δ, ppm: 170.45, 169.86, 169.26, 168.81,
149.55, 149.50, 148.91, 136.96, 123.18, 120.65, 120.41,
85.84, 75.13, 72.68, 70.52, 67.67, 61.52, 20.66, 20.53,
20.51, 20.18.
Preparation of Ru(bpy)2(TAGP-tapy)Cl2. TAGP-
tapy (95.3 mg, 0.2 mmol, 1 eq.) and cis-bis-(2,2'-
bipyridine)dichlororuthenium(II) dihydrate (cis-
Ru(bpy)2Cl2·2H2O) (104.1 mg, 0.2 mmol, 1 eq.) were
suspended in CH2Cl2 : MeOH (1 : 1) and the
suspension was degassed by bubbling with nitrogen for
15 min. The reaction mixture was heated at 100°C for
8 h before being filtered through a hirsch funnel. The
solvent was removed under reduced pressure and the
residue was purified by the silica gel column
chromatography eluting with MeCN : H2O : KNO3 (sat.)
(100 : 7.5 : 0.5). The fraction containing Ru(bpy)2
(TAGP-tapy)Cl2 was collected and the solvent was
evaporated. The resulting solid was dissolved in
CH3CN to remove the excess of KNO3 by filtration to
give the compound as red solid, yield 40.0%. 1H NMR
Synthesis of 2,3,4,6-tetra-O-acetyl-β-D-gluco-
pyranosyl azide (TAGP-N3). TAGP-N3 was prepared
according to the literature procedure [18]. To a solution
of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide
(411.2 mg, 1 mmol, 1.0 eq.) in DMF (10 mL), sodium
azide (78.0 mg, 1.2 mmol, 1.2 eq.) was added and the
reaction mixture was stirred for 4 h. Then it was
diluted with water (50 mL) and extracted with EtOAc
(3×100 mL). The organic layer was dried over Na2SO4
and evaporated to dryness. The residue was purified by
flash chromatography (SiO2, EtOAc–petroleum ether
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 12 2017

SYNTHESIS OF HOMOLEPTIC AND HETEROLEPTIC RUTHENIUM COMPLEXES
3041
spectrum, δ, ppm: 9.45 d (1H), 8.75–7.38 m (20H),
6.14 d.d (1H), 5.51–5.18 m (3H), 4.35–4.15 m (3H),
2.08–1.48 s.s.s.s (12H). 13C NMR spectrum, δ, ppm:
170.81, 170.79, 169.87, 169.75, 157.80, 157.55, 157.46,
157.39, 157.37, 151.81, 151.60, 151.41, 150.39, 148.25,
138.30, 138.03, 137.99, 137.90, 137.67, 127.65, 127.57,
126.92, 126.79, 125.30, 125.25, 124.17, 124.10, 124.00,
123.61, 123.03, 122.93, 86.29, 74.90, 72.09, 70.98,
67.47, 61.40, 19.26, 19.15, 19.08, 18.80.
Following this synthetic approach, different sugar-
functionalized derivatives may be prepared and applied
to various carbohydrate-protein binding studies.
ACKNOWLEDGMENTS
This work was supported by the grant from the Beijing
Natural Science Foundation (2174069) and Scientific
Research Common Program of Beijing Municipal
Commission of Education (KM201510025007). We
would like to thank Prof. Chen-Jie Fang, Prof. Ming
Zhao and Prof. Shiqi Peng for their helpful discussion.
Preparation of Ru(TAGP-tapy)3Cl2. Ruthenium(III)
chloride trihydrate (RuCl3·3H2O) (18.3 mg, 0.07 mmol),
TAGP-tapy (100.1 mg, 0.21 mmol) and N,N-dimethyl-
formamide (DMF; 10 mL) were placed in a 50-mL
flask. The mixture was degassed by bubbling with
nitrogen for 15 min and heated at 160°C for 3 h. The
mixture solution containing the target product was
collected by filtration and concentrated under reduced
pressure. The resulting orange solid was purified by
silica gel column chromatography eluting with
MeCN : H2O : KNO3 (sat.) (100 : 7.5 : 0.5). The
fractions containing the Ru(TAGP-tapy)3Cl2 was
collected, and the solvent was evaporated. The result-
ing solid was dissolved in CH3CN to remove the
excess KNO3 by filtration to give the compound as a
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