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A new family of Ru(ii) complexes with a tridentate pyridine Schiff-base ligand and bidentate co-ligands: synthesis, characterization, structure and in vitro cytotoxicity studies
Electronic Supplementary Material (ESI) for New Journal of Chemistry
This journal is © The Royal Society of Chemistry and The Centre National de la Recherche Scientifique 2013
A New family of Ru(II) complexes with a tridentate pyridine Schiff-base ligand
and bidentate co-ligands. Synthesis, characterization, structure and in vitro
cytotoxicity studies.
Ariadna Garza-Ortiz,a,b Palanisamy Uma Maheswari,a,c Maxime Siegler,d Anthony L. Spekd
and Jan Reedijk.a*
a) Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA
Leiden, The Netherlands. E-mail: reedijk@chem.leidenuniv.nl; Fax: +31 71 527 4671; Tel: +31 71
527 4459.
b) Current address: Departamento de Sistemas Biológicos, Universidad Autónoma MetropolitanaUnidad Xochimilco, Calzada de Hueso 1100, colonia Villa Quietud, 04960, Coyoacán, México.
c) Current address: Department of Chemistry, National Institute of Technology, Tiruchirappalli 620
015, Tamilnadu, India
d) Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University,
Padualaan 8, 3584 CH, Utrecht, The Netherlands.
Table of contents:
1. Table S1 and discussion on IR spectra of the Ru(II) complexes.
2. Figure S1 and ESI-MS analysis.
3. References.
1. Table S1 and discussion on IR spectra of the Ru(II) complexes.
The coordination sphere on all Ru(II)-compounds has been analyzed by means
of FT-IR. The binding mode of the tridentate Schiff base and bidentate moieties to
metal in the complexes have been studied by comparison of IR spectra of
precursors. From IR studies, several changes were observed in the spectra of the
six Ru(II) compounds when comparing with the corresponding spectra obtained
from the starting reagent, [RuCl3(L1)](H2O). Table S1 summarizes the most
important IR peaks, the corresponding assignment and frequencies in the mid-IR
region, confirming the presence of the bis-(arylimino)pyridine ligand, the bidentate
ligand (azpy, bpy, 3mazpy, phen, pic and tazpy) and the chloride ligand all
coordinated to Ru(II).
Table S1. IR assignment of the Ru(II)-complexes spectra. Selected peaks only.
Frequencies (cm
-
(HC=N)
(C=N)pyr
Ru-Npy
Peaks
Ru-Nimin
Ru-Cl
OCOas
ClO4
ClO4
-
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1
)
6
[RuCl3(L1)](H2O)
RuL1-azpy
RuL1-bpy
RuL1-3mazpy
RuL1-phen
RuL1-pic
RuL1-tazpy
-
1595.5
1599
1600
1650
1599
1602
1599
1540
1500-1450
1505-1418
1650-1558
1599-1506
1520
374.3
388
384
376
382
334
388
607-586
590-544
594
524-470
601-590
-
325
318
324
326
328
324
328
1635
1090
1090
1082
1080
1081
A sharp vibration peak assigned to the (Ru-Cl) stretching mode was observed
around 320 cm-1 in all cases and the values are in accordance with the proposed
structures.1, 2, 3 The HC=N(imino)bond stretching vibrations of the tridentate ligand
are present and the shift is associated to metal coordination. The strong band
around 1595 cm-1 in the Ru(III) starting material, is shifted to higher frequency in
the analogues Ru(II) complexes, with the biggest shifts for RuL1-3mazpy. This shift
support the participation of the imino nitrogen in binding to the metal ion.4, 5 The
weak bands between 3200 and 2800 cm -1 are related to (C-H) modes of vibration.
Also, some weak bands located between 2000-1750 cm-1 can be assigned to
overtones of the aromatic rings. The band appearing at 374.3 for [RuCl3(L1)](H2O)6
can be attributed to the (M-N) bond vibration of the pyridine nitrogen. For the
Ru(II) compounds, this vibration peaks present blue shifts and they are consistent
with the proposed changes in the structures. The (M-N) bond vibration of the imino
nitrogen atoms around 600 cm-1 for [RuCl3(L1)](H2O), in the Ru(II) compounds,
presents a red shift. Finally the strong peak around 325 cm -1 is attributed to the RuCl stretching bond vibration.1, 7 Two intense vibrations observed around 1090 and
622 cm-1 are attributed to the presence of the ClO4- anion. As expected they are not
present in RuL1-pic.
The N=N stretching frequency of the coordinated 2-(arylazo)pyridine ligands
is lowered (around 1320 cm-1) compared to that of the free ligand (around 1420
nm). The strong band in the region of 1650-1620 cm-1 is assigned to the
coordinated carboxylate group in the 2-picolinate ligand8-10 in case of RuL1-pic. In
2-picolinic acid, this vibration is observe around 1700 cm -1, and then the decrease
in frequency is due to coordination.11
2. ESI-MS analysis.
622
622
622
622
622
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The mass spectra were measured in the positive mode and in the range of
m/z=200-1200. Ions containing ruthenium presents a clearly visible metal isotope
pattern arising from the distribution, 96Ru 5.52, 98Ru 1.88, 99Ru 12.7, 100Ru 12.6,
101
Ru 17, 102Ru 31.6 and 104Ru 18.7%. For all the perchlorate salts of the Ru(II)
compounds studied, the loss of the perchlorate is the dominant ionization process
observed, this generates a singly charged Ru(II) ion. The positive ion spectra of the
compounds show mainly one major ion. In some cases an ion, which could be
explained as the association of water to the positively charged complex, is also
observed in the spectra. This fragmentation pattern in the ESI mass spectra of
each complex strongly supports the proposed formulation of the complexes. For
RuL1-pic the ion observed corresponds to the addition of one proton and the peaks
exhibit the correct isotopomer distribution. The mass spectra of RuL1-phen is
shown in figures S1.
Figure S1. ESI-MS positive ion spectrum of RuL1-phen (m/z in Da). See experimental
section for calculated data. In the inset: The calculated spectrum for the cation of RuL1phen (m/z in Da).
3. References
1. B. Mondal, M. G. Walawalkar and G. K. Lahiri, J. Chem. Soc.-Dalton Trans., 2000,
4209-4217.
2. B. Mondal, S. Chakraborty, P. Munshi, M. G. Walawalkar and G. K. Lahiri, J. Chem.
Soc.-Dalton Trans., 2000, 2327-2335.
3. T. D. Thangadurai and S. K. Ihm, Transit. Met. Chem., 2004, 29, 189-195.
4. S. Pal and S. Pal, Polyhedron, 2003, 22, 867-873.
5. S. Pal and S. Pal, J. Chem. Soc.-Dalton Trans., 2002, 2102-2108.
6. A. Garza-Ortiz, P. U. Maheswari, M. Siegler, A. L. Spek and J. Reedijk, Inorg. Chem.,
2008, 47, 6964-6973.
Electronic Supplementary Material (ESI) for New Journal of Chemistry
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7. N. C. Pramanik, K. Pramanik, P. Ghosh and S. Bhattacharya, Polyhedron, 1998, 17,
1525-1534.
8. X. J. Yang, F. Drepper, B. Wu, W. H. Sun, W. Haehnel and C. Janiak, Dalton Trans.,
2005, 256-267.
9. A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. Vonzelewsky,
Coord. Chem. Rev., 1988, 84, 85-277.
10. V. G. Vaidyanathan and B. U. Nair, Dalton Trans., 2005, 2842-2848.
11. A. Anthonysamy, S. Balasubramanian, V. Shanmugaiah and N. Mathivanan, Dalton
Trans., 2008, 2136-2143.