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To cite this article: G. Raja, N. Sathya & C. Jayabalakrishnan (2011): Spectroscopic, catalytic, and
biological studies on mononuclear ruthenium(II) ONSN chelating thiosemicarbazone complexes,
Journal of Coordination Chemistry, 64:5, 817-831
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Journal of Coordination Chemistry
Vol. 64, No. 5, 10 March 2011, 817–831
Post Graduate and Research Department of Chemistry, Sri Ramakrishna Mission Vidyalaya
College of Arts and Science, Coimbatore – 641 020, Tamil Nadu, India
1. Introduction
key reaction in organic synthesis. The development of new procedures that can use air
or molecular oxygen as oxidant is environmentally attractive [14]. Research has
described the use of solid-supported heterogeneous catalysts, notably ruthenium-based
for the aerobic oxidation of alcohols [15]. DNA-binding metal complexes have been
extensively studied as DNA structural probes, DNA-dependent electron-transfer
probes, DNA foot printing and sequence-specific cleaving agents, and potential
anticancer drugs [16–18].
Here we report the synthesis, characterization, catalytic, biological, and DNA-
binding activities of Ru(II) complexes containing triphenylphosphine/arsine/pyridine as
coligands. Mixed-chelate complexes of ruthenium have been synthesized using
tetradentate Schiff-base ligands derived by the condensation of salicylaldehyde/o-
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2. Experimental
R3
OH S
R2 + H2 N NH C NH2 + O O
O H
R1
Ethanol
Reflux, 6 h
R3
OH
R2
N S
R1 N O
HN C H
R1 R2 R3 Abbreviation
H H H H2L1
CH3 H H H2L2
H H OCH3 H2L3
H C4H4 H H2L4
FT-IR 8000 spectrometer RX1 model from 4000 to 400 cm1. Electronic spectra of the
complexes were recorded in dichloromethane with a Systronics-2202 double beam
spectrophotometer from 800 to 200 nm. The 1H- and 13C-NMR spectra of the ligands
and complexes were recorded with a Bruker WM 500 DCX MHz instrument using
TMS as an internal standard. 31P NMR spectra were recorded with a Bruker WM 500
DCX MHz instrument using orthophosphoric acid as an internal standard. Mass
spectra were recorded with a JEOL GC make instrument at Indian Institute of
Technology, Chennai. Cyclic voltammetric studies were carried out on a CHN
Instrument in dichloromethane using a glassy carbon working electrode. A platinum
electrode and a saturated calomel electrode were used as counter and reference
electrodes, respectively. Melting points were recorded with a Veego DS Model
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R3
OH
R2 + [RuHCl(CO)(EPh3)2(B)]
N SH N O
R1 N C H
Benzene-Ethanol
Reflux, 6 hrs
R3 CO B
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O
Ru
R2
N S N O
R1 N C H
1.03 cm3 (0.01 mol) of PhBr in anhydrous Et2O (5 cm3) and the free ligands, metal
precursors, and ruthenium complex (0.05 mmol) chosen for investigation were added
and heated under reflux for 6 h. The reaction mixture was cooled and hydrolyzed with a
saturated solution of aqueous NH4Cl and the ether extract on evaporation gave a crude
product of biphenyl which was chromatographed to get pure biphenyl, which was
compared with an authentic sample (m.p. 69–72 C) [24].
UV absorbances at 260 and 280 nm of ca 1.8–1.9 : 1, indicating that the DNA was
sufficiently free of protein [26]. The concentration of CT-DNA per nucleotide was
determined spectrophotometrically ("260 ¼ 6600 (mol L1)1 cm1) [27]. Stock solutions
were stored at 4 C and used within 3 days. Titration experiments were performed at a
fixed complex concentration (20 mm), to which CT-DNA stock solution was added up
to a [DNA]/[Ru] ratio of 1 : 1. The mixture was allowed to equilibrate for 5 min before
spectra were recorded.
3.1.1. FT-IR spectra. FT-IR spectra of the free ligands were compared with those of
the new complexes to confirm coordination of ligand to ruthenium (table 2). The ligand
822 G. Raja et al.
Ligand/complex –C¼N– Ph–C–O –C–S Py max (nm) "max (dm3 mol1 cm1)
can exhibit thione–thiol tautomerism. The FT-IR spectra of the free ligands showed a
band at 1620–1630 cm1 characteristic of the azomethine group (4C¼N), whereas in
complexes this band is slightly shifted to lower frequency at 1600–1619 cm1. This
indicates coordination of the Schiff bases through the azomethine nitrogen [28]. The
band of medium intensity at 1059–1061 cm1 in all ligands may be assigned to C¼S
stretch. In spectra of the complexes, this band disappears and a new band appears at
737–746 cm1, attributed to enolization of the –NH–C¼S group and subsequent
coordination through deprotonated sulfur [29]. For the ligands, strong bands at 681–
705 cm1 are due to the furan ring. On complexation, there is no change in the furan
ring owing to the non-involvement of the hetero atom in coordination. A strong band
due to phenolic C–O was observed at 1263–1277 cm1 in the ligands, shifted to higher
frequency (1282–1357 cm1) in the complexes, showing that the other coordination site
was through the phenolic oxygen [30–32]. This was further supported by the
disappearance of the broad band at 3219 cm1 due to phenolic OH in the complexes.
For all the complexes, IR spectra showed a strong band at 1930–1952 cm1 due to a
terminally coordinated carbonyl. For [Ru(CO)(Py)(L1)], [Ru(CO)(Py)(L2)],
[Ru(CO)(Py)(L3)], and [Ru(CO)(Py)(L4)], IR spectra showed a medium intensity
band at 1025–1032 cm1 characteristic of coordinated nitrogen base [22]. Characteristic
bands for triphenylphosphine/arsine were also present in the expected region 1428–
1435 cm1 [33].
3.1.2. Electronic spectra. Electronic absorption spectra of the free ligands and their
complexes in CH2Cl2 are listed in table 2. Spectra of all the free ligands showed two
types of transition at 303–308 and 363–406 nm due to –* and n–* transitions
involving the benzene ring, –C¼N, and enolic S–H. These bands were shifted in spectra
of the complexes, indicating the involvement of imine group nitrogen and thionyl sulfur
in coordination with the central metal. Spectra of the complexes showed three to four
Thiosemicarbazone complexes 823
1
Table 3. H-NMR data of ligands and Ru(II) Schiff-base complexes.
1
Ligand/complex H-NMR spectra
H 2L 1 6.6–8.2 (Ar, m), 8.4 (H–C¼N, s), 11.3 (SH, s), 9.9 (Ph–OH, s)
H 2L 2 6.5–8.0 (Ar, m), 8.6 (H–C¼N, s), 11.9 (SH, s), 10.5 (Ph–OH, s), 1.9 (–CH3–C¼N, s)
H 2L 3 6.8–7.9 (Ar, m), 8.4 (H–C¼N, s), 11.4 (SH, s), 9.2 (Ph–OH, s), 3.8 (–OCH3, s)
H 2L 4 7.2–8.6 (Ar, m), 9.0 (H–C¼N, s), 11.4 (SH, s), 10.5 (Ph–OH, s)
[RuCO(PPh3)L1] 6.5–7.9 (Ar, m), 8.4 (H–C¼N, s)
[RuCO(PPh3)L2] 6.5–7.8 (Ar, m), 8.4 (H–C¼N, s), 2.0 (–CH3–C¼N, s)
[RuCO(PPh3)L3] 6.9–7.7 (Ar, m), 8.5 (H–C¼N, s), 3.7 (–OCH3, s)
[RuCO(PPh3)L4] 6.6–8.3 (Ar, m), 8.8 (H–C¼N, s)
[RuCO(AsPh3)L1] 6.5–7.9 (Ar, m), 8.1 (H–C¼N, s)
[RuCO(AsPh3)L2] 6.6–8.0 (Ar, m), 8.5 (H–C¼N, s), 2.0 (–CH3–C¼N, s)
[RuCO(AsPh3)L3] 6.9–7.9 (Ar, m), 8.4 (H–C¼N, s), 3.5 (–OCH3, s)
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bands at 252–484 nm. All Schiff-base ruthenium complexes were diamagnetic, indicat-
ing the presence of ruthenium(II). The ground state of ruthenium(II) in an octahedral
environment is 1A1g and the excited states corresponding to t2g5eg1 configuration
are 3T1g, 3T2g, 1T1g, and 1T2g. Hence, four bands corresponding to the transitions
1
A1g ! 3T1g, 1A1g ! 3T2g, 1A1g ! 1T1g, and 1A1g ! 1T2g are possible in the order of
increasing energy. The high-intensity bands at 252–349 nm were characterized as ligand-
centered bands, designated as –* and n–* transitions for electrons localized on the
azomethine of the Schiff base. The band at 355–484 nm has been assigned to the spin-
allowed 1A1g ! 1T1g transition, based on the low-extinction coefficient values (") as
compared to charge-transfer bands [34–37]. The pattern of the electronic spectra for
the complexes indicates the presence of an octahedral environment around the
ruthenium(II) similar to other ruthenium octahedral complexes [30, 34, 36, 37].
3.1.3. 1H-NMR spectra. 1H-NMR spectra of ligands and complexes were recorded in
DMSO-d6 to confirm the binding mode of the Schiff base to ruthenium ion; the values
are given in table 3 (Supplementary material). Aromatic protons for the ligands appear
as multiplets at 6.5–8.6 ppm. The H–C¼N, –SH, and Ph–OH protons appear as singlets
at 8.4–9.0, 11.3–11.9, and 9.2–10.5 ppm for all the Schiff bases. In H2L2, the azomethine
methyl protons are a singlet at 1.9 ppm. The methoxy protons of H2L3 are a singlet at
3.8 ppm. On complexation, a multiplet at 6.5–8.6 ppm is assigned to aromatic protons,
triphenylphosphine/arsine, and pyridine protons. The azomethine proton signals in the
complexes are at 8.1–9.1 ppm, shifted on complexation indicating coordination through
the azomethine nitrogen to metal ion. The azomethine methyl protons are a singlet at
2.0 ppm for [Ru(CO)(PPh3)L2], [Ru(CO)(AsPh3)L2], and [Ru(CO)(Py)L2], while
methoxy protons of [Ru(CO)(PPh3)L3], [Ru(CO)(AsPh3)L3], and [Ru(CO)(Py)L3] are
a singlet at 3.5–3.7 ppm. The absence of Ph–OH and –SH resonance in the complexes
indicates the deprotonation of phenol and thiol of the Schiff base on complexation and
coordination to ruthenium through phenolic oxygen and thiolic sulfur.
824 G. Raja et al.
13
Table 4. C-NMR spectra of Ru(II) Schiff-base complexes.
13
Ligand/complex C-NMR spectra
3.1.4. 13C-NMR spectra. 13C-NMR data were recorded in CDCl3 solution and the
assignments of ligands and complexes are listed in table 4 (Supplementary material).
13
C-NMR spectra of H2L1–H2L4 display a single resonance at 148–157 ppm for
azomethine carbons, which confirms the structure of ligands. The thiolic carbon of the
Schiff bases appeared at 131–143 ppm. The signal due to the methyl carbon of H2L2 and
methoxy carbon of H2L3 appear at 19 and 56 ppm, respectively. The aromatic carbons
for all the ligands appear at 112–132 ppm. For [Ru(CO)(PPh3)L4], [Ru(CO)(AsPh3)L1],
[Ru(CO)(AsPh3)L2], and [Ru(CO)(Py)L3], aromatic carbons appear at 126–135 ppm.
The thiolic carbon and azomethine carbons appear at 123–126 and 135–148 ppm [38],
respectively. The signals due to methyl carbon of [Ru(CO)(AsPh3)L2] and methoxy
carbon of [Ru(CO)(Py)L3] appear at 19 and 55 ppm, respectively. For all complexes, the
terminal carbonyl group appears at 175–180 ppm [39].
3.1.5. 31P-NMR spectra. 31P-NMR spectra were recorded for two complexes to
confirm the presence of triphenylphosphine and to determine the geometry of the
complexes. [Ru(CO)(PPh3)L4] has one signal at 28.62 ppm, confirming the presence of
only one triphenylphosphine.
3.1.6. Mass spectra. The mass spectrum of [RuCO(Py)L2] was recorded and the
appearance of molecular ion peak at 493.65 confirms the proposed molecular formula
of the complex. The mass spectrum of the complex is shown in Supplementary material.
RuIII–RuII RuII–RuI
Complex Epc (V) Epa (V) Ef (V) DEP (mV) Epc (V) Epa (V) Ef (V) DEP (mV)
complexes on to the electrode surface [41]. The reason for the irreversibility observed
for the reductive response of the complexes may be due to a short-lived reduced state of
the metal ion or due to the oxidative degradation of the ligands [42]. The different redox
behavior of the complexes can be accredited to the different substituents present in the
thiosemicarbazone ligands [43]. From the electrochemical data, the present system
stabilizes the higher oxidation state of ruthenium.
826
[RuHCl(CO)(PPh3)3] 0.108 11.22 21.9 22.7 19.2 20.0 16.1 21.4 18.6 20.6
[RuHCl(CO)(AsPh3)3] 0.105 10.91 21.2 22.0 18.2 18.9 15.1 20.1 17.5 19.4
[RuHCl(CO)(Py)(PPh3)2] 0.100 10.39 20.2 20.9 17.5 18.2 14.1 18.7 16.3 18.0
H2L1 0.097 9.34 17.9 18.2 16.3 17.1 11.3 14.98 14.3 15.8
H2L2 0.103 9.91 19.7 20.6 17.3 18.1 14.0 15.9 15.8 17.5
H2L3 0.101 9.72 18.6 19.4 16.6 17.4 12.8 16.9 14.9 16.5
H2L4 0.092 8.85 17.5 18.2 15.7 16.4 11.6 15.4 12.3 13.6
[RuCO(PPh3)L1] 0.242 23.29 61.73 64.47 57.90 60.50 44.3 58.9 49.88 55.34
G. Raja et al.
[RuCO(PPh3)L2] 0.396 38.11 79.5 83.08 67.55 70.55 46.63 62.08 52.7 58.5
[RuCO(PPh3)L3] 0.440 42.35 66.5 69.5 65.36 68.27 44.6 59.4 51.00 56.5
[RuCO(PPh3)L4] 0.239 23.00 60.36 68.27 56.91 59.44 42.88 57.09 47.00 52.15
[RuCO(AsPh3)L1] 0.443 42.63 63.82 66.65 56.90 59.44 45.25 60.25 48.13 53.40
[RuCO(AsPh3)L2] 0.533 51.30 71.73 74.93 66.80 69.12 45.63 60.75 50.25 55.76
[RuCO(AsPh3)L3] 0.498 47.93 67.73 70.74 65.46 68.36 46.25 61.59 52.00 57.7
[RuCO(AsPh3)L4] 0.396 38.11 60.73 63.43 51.91 54.22 42.50 56.59 46.2 51.32
[RuCO(Py)L1] 0.218 20.98 64.82 67.70 58.91 61.53 43.25 57.59 49.13 54.51
[RuCO(Py)L2] 0.421 40.52 69.73 72.83 67.91 70.93 46.88 62.42 51.25 56.87
[RuCO(Py)L3] 0.309 29.74 62.64 65.42 61.36 64.09 44.25 58.92 50.63 56.18
[RuCO(Py)L4] 0.297 28.58 64.81 67.70 42.82 44.72 43.25 57.59 48.75 54.96
a
Moles of product per mole of catalyst.
Thiosemicarbazone complexes 827
the presence of electron-donating methyl and methoxy enhances the catalytic activity of
acetophenone and o-vanillin complexes over the other two, in agreement with earlier
observations [46]. However, there is a report in which the catalytic activity is increased
by electron-donating substituent [47, 48]. The relatively higher product yield
obtained for the oxidation of benzyl alcohol compared with the other alcohols is
because the -CH of benzyl alcohol is more acidic than cyclohexanol, 1-propanol,
and butane-1-ol [49].
3.3.2. Aryl–aryl coupling reaction. The free ligands, metal precursors, and new
ruthenium(II) complexes have been used as catalysts for phenyl–phenyl coupling; the
results are summarized in table 6. The system chosen for study is the coupling of phenyl
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Table 7. Antibacterial studies of metal precursors, ligands and Ru(II) Schiff-base complexes.
[RuHCl(CO)(PPh3)3] – 5 7 9 2 5 6 6
[RuHCl(CO)(AsPh3)3] 3 5 9 9 4 7 7 8
[RuHCl(CO)(Py)(PPh3)2] 5 6 7 10 5 7 9 11
H 2L 1 5 12 18 23 – 13 5 8
H 2L 2 8 14 23 29 – – 5 10
H 2L 3 10 15 19 28 4 7 12 14
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H 2L 4 12 17 21 25 3 8 15 21
[RuCO(PPh3)L1] 10 13 18 25 5 10 14 20
[RuCO(PPh3)L2] 15 21 30 32 6 12 16 20
[RuCO(PPh3)L3] 10 17 25 28 8 14 20 28
[RuCO(PPh3)L4] 5 8 18 23 – – – –
[RuCO(AsPh3)L1] 8 15 19 23 5 9 14 23
[RuCO(AsPh3)L2] 12 19 25 31 8 14 21 29
[RuCO(AsPh3)L3] 10 17 23 29 9 15 24 31
[RuCO(AsPh3)L4] 7 13 18 23 10 18 26 32
[RuCO(Py)L1] 7 13 18 26 12 20 20 35
[RuCO(Py)L2] 13 20 25 30 8 15 21 29
[RuCO(Py)L3] 10 18 25 29 9 13 21 27
[RuCO(Py)L4] – – – – 9 14 20 26
Amikacin 20 22 23 26 19 21 23 26
1.20
1.18 a
η/η0, Relative specific viscosity
b
1.16
1.14
1.12
1.10
1.08
1.06
1.04
1.02
1.00
0 10 20 30 40 50
µ10–3
1/R = {[Ru-complex]/[DNA]}
Figure 2. The effect of (a) [RuCO(PPh3)L2] and (b) CT-DNA on the viscosity of CT-DNA at 1/R ¼ 0.5
relative viscosity vs. 1/R.
4. Conclusion
absorption titration studies and viscosity measurements, it can be concluded that the
complexes bind to CT-DNA through intercalation.
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Thiosemicarbazone complexes 831