Ruthenium(II/III) bipyridine complexes incorporating thiol-based imine functions: Synthesis, spectroscopic and redox properties

Article abstract of DOI:10.1016/S0277-5387(99)00204-1

A group of five new ruthenium(II) bipyridine heterochelates of the type [Ru^II(bpy)₂L]⁺ 1a-1e have been synthesized (bpy=2,2′-bipyridine; L=anionic form of the thiol-based imine ligands, HS-C₆H₄N=C(H)C₆H₄(R) (R=OMe, Me, H, Cl, NO₂). The complexes 1a-1e are 1:1 conducting and diamagnetic. The complexes 1a-1e exhibit strong MLCT transitions in the visible region and intra-ligand transitions in the UV region. In acetonitrile solvent complexes show a reversible ruthenium(III)-ruthenium(II) couple in the range 0.2-0.4 V and irreversible ruthenium(III)→ruthenium(IV) oxidation in the range 1.15-1.73 V vs. SCE. Two successive bipyridine reductions are observed in the ranges -1.43 to -1.57 and -1.67 to -1.78 V vs. SCE. The complexes are susceptible to undergo stereoretentive oxidations to the trivalent ruthenium(III) congeners. The isolated one-electron paramagnetic ruthenium(III) complex, 1c⁺ exhibits weak rhombic EPR spectrum at 77 K (g₁=2.106, g₂=2.093, g₃=1.966) in 1:1 chloroform-toluene. The EPR spectrum of 1c⁺ has been analyzed to furnish values of distortion parameters (Δ=8988 cm^-1; V=0.8833 cm^-1) and energy of the expected ligand field transitions (ν₁=1028 nm and ν₂=1186 nm) within the t₂ shell. One of the ligand field transitions has been experimentally observed at 1265 nm. Elsevier Science Ltd.

Full text of DOI:10.1016/S0277-5387(99)00204-1

Polyhedron 18 (1999) 2951–2959
www.elsevier.nl/locate/poly
Ruthenium(II/III) bipyridine complexes incorporating thiol-based imine
functions
Synthesis, spectroscopic and redox properties
*
Debadeep Bhattacharyya, Soma Chakraborty, Pradip Munshi, Goutam Kumar Lahiri
Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400076, India
Received 31 March 1999; accepted 7 July 1999
Abstract
A group of five new ruthenium(II) bipyridine heterochelates of the type [RuII(bpy)2L]1 1a–1e have been synthesized (bpy52,29-
bipyridine; L5anionic form of the thiol-based imine ligands, HS–C6H4N=C(H)C6H4(R) (R5OMe, Me, H, Cl, NO2). The complexes
1a21e are 1:1 conducting and diamagnetic. The complexes 1a21e exhibit strong MLCT transitions in the visible region and intra-ligand
transitions in the UV region. In acetonitrile solvent complexes show a reversible ruthenium(III)–ruthenium(II) couple in the range 0.2–0.4
V and irreversible ruthenium(III)→ruthenium(IV) oxidation in the range 1.15–1.73 V vs. SCE. Two successive bipyridine reductions are
observed in the ranges 21.43 to 21.57 and 21.67 to 21.78 V vs. SCE. The complexes are susceptible to undergo stereoretentive
oxidations to the trivalent ruthenium(III) congeners. The isolated one-electron paramagnetic ruthenium(III) complex, 1c1 exhibits weak
rhombic EPR spectrum at 77 K (g152.106, g252.093, g351.966) in 1:1 chloroform–toluene. The EPR spectrum of 1c1 has been
analyzed to furnish values of distortion parameters (D58988 cm21; V50.8833 cm21) and energy of the expected ligand field transitions
(n151028 nm and n251186 nm) within the t2 shell. One of the ligand field transitions has been experimentally observed at 1265 nm.
1999 Elsevier Science Ltd. All rights reserved.
Keywords: Ruthenium(II/III) bipyridine complexes; Schiff base ligand; Spectroscopic and electrochemical properties
1. Introduction
based anionic Schiff-base ligand. The ligand L can act as
both a s- and a p-donor in contrast to the s-donor but
p-acceptor nature of bipyridine molecule. Herein we report
the synthesis of a group of new ruthenium–bipyridine
complexes having a RuN5S chromophore, their spectro-
scopic and electrochemical properties and the electronic
structure of the trivalent congener. To the best of our
knowledge this work demonstrates the first example of
[RuII / III(byp)2L]11 / 21 complexes where L is a thiol-based
Schiff base ligand.
Since the discovery of important photo-redox activities
of ruthenium complexes incorporating 2,29-bipyridine lig-
and, there has been continuous research activity in the
direction of developing new ruthenium–bipyridine com-
plexes with the perspective of tuning the redox and
photophysical functions of this class of complexes [1–16].
Basic strategies behind all these activities are either to
introduce selective groups within the bipyridine moiety
itself or use other types of donor sites along with the
ruthenium–bipyridine core to generate new mononuclear
or polynuclear mixed ligand complexes to modulate the
photo-redox activities [17–33]. The present work origi-
nates from our interest in developing new hetero
ruthenium–bipyridine tris complexes of the type
[RuII / III(byp)2L]11 / 21 where L is an electron-rich thiol-
2. Experimental
2.1. Materials
Commercially available ruthenium trichloride (S.D. Fine
Chemicals, Bombay, India) was converted to RuCl3 –3H2O
by repeated evaporation to dryness with concentrated
hydrochloric acid. The starting complex [RuII(bpy)2Cl2]?
2H2O was prepared according to the reported procedure
*Corresponding author. Tel.: 191-22-576-7159; fax: 191-22-578-
3480.
E-mail address: lahiri@ether.chem.iitb.ernet.in (G.K. Lahiri)
0277-5387/99/$ – see front matter
PII: S0277-5387(99)00204-1
1999 Elsevier Science Ltd. All rights reserved.

2952
D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
[34]. The compounds 2-amino thiophenol and p-substituted
benzaldehydes were obtained from Fluka, Switzerland.
Other chemicals and solvents were reagent grade and used
as received. Silica gel (60–120 mesh) used for the column
chromatography was purchased from S.D. Fine Chemicals,
Bombay, India. For spectroscopic and electrochemical
studies HPLC-grade solvents were used. Commercial
tetraethyl ammonium bromide was converted to pure
tetraethyl ammonium perchlorate (TEAP) by following an
available procedure [35].
observed near-IR result clearly eliminates this solution as
unacceptable.
2.4. Synthesis of ligands (HL1 –HL5) and complexes
1a–1e
The ligands HL1–5 were prepared by condensing 2-
aminothiophenol with the appropriate benzaldehyde in dry
ethanol under ice-cold conditions. The use of dry ethanol is
absolutely essential to get the desired ligands in the pure
solid state.
The complexes 1a–1e were synthesized using a general
method. Yields varied in the range 55–60%. Specific
details are given for one representative case, 1c.
2.2. Physical measurements
Solution electrical conductivity was checked using a
Systronic conductivity bridge, 305. Electronic spectra
(900–200 nm) were recorded using a Shimadzu UV 160
spectrophotometer. The near-IR spectrum was recorded by
using a Hitachi 330 spectrophotometer. Infrared spectra
were taken on a Nicolet spectrophotometer with samples
prepared as KBr pellets. Magnetic susceptibility was
2.4.1. Bis(2,29-bipyridine)(N-phenylthiosalicylaldimine)
ruthenium(II) perchlorate dihydrate [RuII(bpy)2L3]ClO4?
2H2O (1c)
The starting complex RuII(bpy)2Cl2?2H2O (300 mg,
0.57 mmol) was dissolved in absolute ethanol (20 cm3)
and to this 468 mg (2.28 mmol) of AgClO4 was added and
the mixture was refluxed for 30 min. It was then cooled
and filtered through a sintered glass crucible. To this
filtrate 240 mg (1.13 mmol) of HL3 and 93 mg (1.13
mmol) of anhydrous sodium acetate were added and the
resulting mixture was stirred under a nitrogen atmosphere.
The stirring was continued overnight and the resultant
product was cooled for about 4 h and then filtered. The
solid product thus obtained was washed thoroughly with
ice-cold water and dried in a vacuum desiccator over
P4O10. The crude product was purified by column chroma-
tography using a silica-gel column. The excess ligand was
initially eluted with benzene. The desired deep brown
colored complex 1c was then eluted using a 3:1 dichloro-
methane–acetonitrile mixture. On removal of the solvent
under reduced pressure the complex 1c was obtained in the
solid state. The product was then further purified by
recrystallization from dichloromethane–hexane (1: 4). The
yield was 58%.
1
checked with a PAR vibrating-sample magnetometer. H
NMR spectra were obtained using a 300 MHz Varian
FT-NMR spectrometer. Cyclic voltammetry and coulomet-
ric measurements were carried out using a PAR model
273A electrochemistry system. A platinum-wire working
electrode, a platinum-wire auxiliary electrode and an SCE
reference electrode were used in a three-electrode configu-
ration. TEAP was the supporting electrolyte and the
solution concentration was |1023 M. The half-wave
potential E2098 was set equal to 0.5 (Epa1Epc), where Epa
and Epc are anodic and cathodic cyclic voltammetric peak
potentials, respectively. The scan rate used was 50 mV s21
.
A platinum-wire gauze working electrode was used in
coulometric experiments. All electrochemical experiments
were carried out under a dinitrogen atmosphere and are
uncorrected for junction potentials. EPR measurements
were made using a Varian model 109 E-line X-band
spectrometer fitted with a quartz dewar for measurements
at 77 K (liquid nitrogen). The spectrum was calibrated by
using tetracyanoethylene (tcne, g52.0023). The elemental
analyses were carried out with a Carlo Erba (Italy)
elemental analyzer. The following Hammett s values for
p-substituents were used: H, 0.00; Me, 20.17; OMe,
20.27; Cl, 10.23; NO2, 10.78 [36].
2.4.2. Bis(2,29-bipyridine)(N-phenylthiosalicylaldimine)
ruthenium(III) diperchlorate dihydrate
[RuIII(bpy)2L3](ClO4 )2?2H2O (1c1)
[RuII(bpy)2L3]ClO4?2H2O (100 mg) was dissolved in
acetonitrile (25 cm3) and excess aqueous ceric ammonium
sulfate solution was added to it. The mixture was stirred
vigorously for 2 h. The color changed from deep brown to
bluish green. The volume of the oxidized solution was
reduced under vacuum. An aqueous solution of saturated
sodium perchlorate was added to the concentrated solution
and the mixture was kept in the refrigerator for 2 h. The
solid compound thus obtained was filtered under high
vacuum and washed with ice-cold water followed by cold
methanol. The solid mass was finally dried in vacuo over
P4O10. Yield: 95 mg (85%).
Caution: Perchlorate salts of metal complexes are
generally explosive. Care should be taken while handling
such complexes.
2.3. Treatment of EPR data
An outline of the procedure can be found in our recent
publications [37,38]. We would like to note that a second
solution also exists that is different from the chosen one,
having small D, n1 and n2 values. The experimentally

D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
2953
3. Results and discussion
from the reaction mixture as their dihydrated perchlorate
salts and the crude products were purified by column
chromatography using a silica-gel column.
3.1. Synthesis and characterization
The use of an inert atmosphere during the synthesis of
the complexes (1a–1e) is found to be essential as the
presence of atmospheric oxygen facilitates the formation of
the oxidized trivalent congener of 1.
The microanalytical data of the complexes (Table 1) are
in good agreement with the calculated values, thus con-
firming the gross composition of the mixed tris chelates
[Ru(byp)2L]ClO4?2H2O (1a21e). The complexes exhibit
1:1 conductivity in acetonitrile solution (Table 1) and all
the monocations are essentially diamagnetic.
A group of five substituted thiol-based Schiff base
ligands used are abbreviated as HL1–HL5. The deproto-
nated form of HL binds to the metal ion in a bidentate S, N
manner forming a five-membered chelate ring. The com-
plexes 1 have been synthesized from [Ru(bpy)2Cl2]?2H2O
following the synthetic route shown in Scheme 1.
The complex cations (1a–1e) were precipitated directly
3.2. Spectra
The n(C=N) stretching frequency of the free ligands
(HL) appears near 1620 cm21 which has been shifted to
1590 cm21 (Table 1) in accordance with the coordination
of the azomethine function to the metal ion [39]. A very
strong and broad band near 1100 cm21 and a strong and
sharp vibration band near 630 cm21 are observed for all
the complexes (Table 1) due to the presence of ionic
perchlorate.
1
The H NMR spectra of the complexes were recorded in
(CD3)2 SO solvent using a 300 MHz instrument. The
spectra of one representative complex (1d) is shown in
Scheme 1. (i) AgClO4, EtOH, heat, stirring; (ii) HL, NaO2CMe, N2,
stirring.
Table 1
Microanalyticala, conductivityb, infraredc and electronicb spectral data
Compound
Elemental analysis (%)
LM /V21
IR (cm21
)
UV–Vis
(cm2 mol21
)
lmax (nm) (´d, M21 cm21
)
C
H
N
n(C=N)
n(ClO24 )
1a
64.51
(64.39)
5.17
(5.08)
2.13
(2.20)
145
150
147
155
145
235
1593
1100, 610
618(1603)e, 498(4800),
428(4800), 335(25000),
318(37200)e, 296(58400),
250(34600), 217(50000)
625(1100)e, 483(3330),
430(4798), 331(7450),
285(12998), 246(7598),
208(17066)
1b
1c
66.18
(66.06)
5.31
(5.22)
2.39
(2.27)
1594
1595
1591
1595
1590
1100, 620
1097, 621
1091, 623
1095, 620
1110, 625
65.50
(65.61)
5.10
(5.00)
2.42
(2.32)
630(2000)e, 490(5340),
430(5330), 350(7400)e,
290(33800), 240(30100),
220(41400)
1d
1e
62.21
(62.07)
4.51
(4.57)
2.32
(2.19)
687(4233)e, 491(7102),
432(7170), 330(13387),
280(46000), 243(41280),
205(46000)
61.19
(61.06)
4.57
(4.50)
4.45
(4.31)
696(1980)e, 535(2795),
441(4283), 364(5125),
287(38279), 252(27544),
213(32150)
1c1
56.44
(56.34)
4.34
(4.29)
2.16
(1.99)
605(6270), 415(15026),
305(35030), 220(35110)
a Calculated values are in parentheses.
b In acetonitrile.
c In KBr disk.
d Extinction coefficient.
e Shoulder.

2954
D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
Fig. 1. 1H NMR spectrum of [Ru(bpy)2L4]ClO4?2H2O, 1d in (CD3)2SO.
Fig. 1. The presence of asymmetric ligand L in the
complexes (1a–1e) makes all the six aromatic rings
inequivalent. The complexes 1c and 1a, 1b, 1d, 1e thus
possess 25 and 24 non-equivalent aromatic protons, re-
spectively. Since the electronic environment of many
aromatic hydrogen atoms are similar, their signals appear
in a narrow chemical shift range. In fact the aromatic
regions of the spectra are complicated due to the overlap-
ping of several signals which have precluded the identifica-
tion of individual resonances. However, direct comparisons
of the intensity of the aromatic region proton signals with
that of the clearly observable azomethine proton (–CH=N–)
in the downfield region [d(–CH=N–), |9.2 ppm] and with
the aliphatic protons for the complexes 1a (–OCH3; d,
3.32 ppm and 1b –Me; d, 2.51 ppm) reveal the presence of
the expected number of aromatic protons for all the
complexes. The singlet due to the azomethine (–CH=N–)
proton in the complexes 1a–1e is found to be considerably
deshielded, d.9 ppm relative to that of the free ligands,
d|8.5 ppm as a consequence of electron donation to the
metal center [40].
The electronic spectra of the complexes (1a–1e) were
recorded in acetonitrile solvent in the region of 200–900
nm. The spectral data are listed in Table 1 and the
representative spectrum is shown in Fig. 2. The complexes
exhibiting multiple absorptions in the UV–visible region.
In the visible region the complexes primarily display two
moderately intense transitions near 500 and 430 nm. The
lowest energy band is associated with a shoulder near 600
nm. The bands near 500 nm and 430 nm can be assigned to
dp(Ru)→p*(bpy) (symmetric) and dp(RuII)→p*(bpy)
(antisymmetric) MLCT (metal-to-ligand charge-transfer)
transitions [41–44]. The next highest energy band near 350
nm may be due to the dp(RuII)→L MLCT transition. The
higher energy bands in the UV region are of intra-ligand
p–p* type or charge-transfer transitions involving energy
levels which are higher in energy than the ligand lowest
unoccupied molecular orbital (LUMO).
It may be noted that for the Ru(bpy)231 complex the
lowest energy MLCT transition takes place at 450 nm in
acetonitrile solution [45], which has reasonably red shifted
(|500 nm) on substitution of one bipyridine ligand by the
L. This is possibly due to the greater s-donor and weaker
p-acceptor properties of L2 compared to bpy.
3.3. Electron transfer properties
The electron transfer properties of the complexes have
been studied by cyclic voltammetry and differential pulse
voltammetry using a platinum-wire working electrode. All
complexes systematically display four redox processes in
the potential range of 62 V vs. the saturated calomel
electrode (SCE). Representative voltammograms are dis-
played in Fig. 3 and the reduction potentials data are
shown in Table 2.
3.3.1. Metal redox
The complexes (1a–1e) display one reversible couple in
the range 0.26–0.4 V vs. SCE (Fig. 3) which is assigned to
the ruthenium(III)–ruthenium(II) process Eq. (1). The
one-electron nature of the couple is

D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
2955
Fig. 2. Electronic spectrum of [Ru(bpy)2L3]ClO4?2H2O, 1c in acetonitrile.
[RuIII(bpy)2(L)]21 1 e2 á [RuII(bpy)2(L)]11
(1)
the couple (Eq. 1) varies depending on the electronic
nature of the substituents present in the ligand frame, as
expected (Table 2), and a plot of E1 / 2 vs. sR is linear (Fig.
3) [46], where sR is the Hammett constant of the sub-
stituent R. Under identical experimental conditions, the
ruthenium(III)–ruthenium(II) couple of Ru(bpy)231 ap-
confirmed by constant potential coulometry (Table 2). The
presence of trivalent ruthenium in the oxidized solution is
established by the characteristic EPR spectrum of the
ruthenium(III) congener (see later). The formal potential of
Fig. 3. Cyclic voltammograms of |1023 M solution of [Ru(bpy)2L1]ClO4?2H2O, 1a in acetonitrile at 298 K (——). Differential pulse voltammograms are
shown for the oxidation processes only (--------). Inset shows the least-squares fit of E1 / 2 of the RuIII–RuII couple vs. sR.

2956
D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
Table 2
Electrochemical data at 298 Ka
Compound
RuII–RuIII couple,
RuIII–RuIV
Epa (V)
Ligand reduction
c
E0298 (V) [DEp (mv)]
nb
E0298(V) [DEp(mv)]
1a
1b
1c
1d
1e
0.26 (60)
0.28 (70)
0.31 (70)
0.34 (65)
0.40 (65)
1.09
1.11
0.95
1.07
1.10
1.15
1.41
1.54
1.64
1.73
21.57(100)
21.54 (95)
21.51(90)
21.45(100)
21.43(100)
21.78(110)
21.74(100)
21.72(110)
21.71(120)
21.67(120)
a Condition: solvent, acetonitrile; supporting electrolyte, TEAP; reference electrode, SCE; solute concentration, |1023 M; working electrode, platinum
wire.
b n 5 Q/Q1 where Q1 is the calculated Coulomb count for 1 e2 transfer and Q is the Coulomb count found after exhaustive electrolysis of |1022
M
solution of the complex.
c Epa values are considered due to the irreversible nature of the voltammograms.
pears at 1.29 V [43]. Thus, replacement of one p-acidic
bpy ligand from the Ru(bpy)231 core by one s-donating
anionic thiolato ligand L2 results in a decrease of the
ruthenium(III)–ruthenium(II) potential by 0.9–1.0 V de-
pending on the nature of the R group in the ligand frame
(L). The reduction of the overall charge of the complex
cation from 12 in Ru(bpy)231to 11 in the present set of
complexes (1a–1e) provides further electrostatic stabiliza-
tion of the oxidized trivalent ruthenium(III) congener
which has possibly originated from the better s-donor and
weaker p-acceptor character of L2 [47].
The low ruthenium(II)–ruthenium(III) oxidation poten-
tial in the complexes (1a–1e) might be responsible for the
preferential stabilization of the complexes in the trivalent
ruthenium(III) oxidation state if the reaction is carried out
under atmospheric conditions as stated before [48].
The complexes exhibit a second irreversible oxidation
process in the range 1.15–1.73 V vs. SCE (Fig. 3).
Although the current height of this process is found to be
|1.6 times more than that of the previous ruthenium(III)–
ruthenium(II) couple, the one-electron nature of the second
irreversible oxidation process has been established by
differential pulse voltammetry (Fig. 3). The second oxida-
tion process might be due to either RuIII→RuIV oxidation
or oxidation of the coordinated thiolato function. Since the
observed potential difference between the two successive
oxidation processes (RuII / III, second irreversible oxidation
process) in the complexes (1a–1e) (0.9–1.3 V, Table 2)
compares well with the reported RuII / III–RuIII / IV potential
difference in many mononuclear complexes [49,50], it may
be reasonable to consider the second oxidation process as
ruthenium(III)→ruthenium(IV) oxidation, Eq. (2). How-
ever, the possibility of the oxidation of coordinated
case of the ruthenium(III)–ruthenium(IV) oxidation pro-
cess compared to the ruthenium(II)–ruthenium(III) oxida-
tion process (Table 2).
3.3.2. Ligand reduction
The complexes display two quasi-reversible reductions
in the ranges 21.43 to 21.57 and 21.67 to 21.78 V
(Table 2, Fig. 3). The one-electron nature of the couples
has been established by the current height considerations.
Since the free ligands HL do not exhibit any ligand
reductions within the above-mentioned potential range, the
observed reductions are therefore considered to be two
successive reductions of the coordinated bpy ligands. Since
each bpy can accept two electrons in its lowest unoccupied
molecular orbitals (LUMO) [51–54], four such reduction
steps are expected for each of the complexes (1a–1e).
However, only two reductions corresponding to Eqs. (3)
and (4) have been observed within a 22 V potential range.
[RuII(bpy)2(L)]1 1 e2 á [RuII(bpy)(bpy?2)(L)]
[RuII(bpy)(bpy?2)(L)] 1 e2 á [RuII(bpy?2)(bpy?2)(L)]2
(3)
(4)
The two other expected reductions could not be detected,
possibly due to solvent cut-off.
3.4. Electrogeneration of trivalent ruthenium congeners
and distortion parameters
Coulometric oxidations of the complexes in acetonitrile
solvent at a potential of 100 mV positive to the corre-
sponding Epa of the RuIII–RuII couple produced the deep
bluish green colored trivalent-ruthenium(III) complexes.
The observed Coulomb count corresponds to 1e2 transfer
for all the complexes (Table 2). The oxidized solutions
(1a1–1e1) show the voltammograms which are superim-
posable on those of the corresponding bivalent complexes
(1a–1e), indicating the stereoretentive nature of the oxida-
tion process [55]. The electrochemical rereductions of the
oxidized bluish green solutions (11) at 0.0 V regenerated
the corresponding bivalent complexes 1 quantitatively. The
[RuIII(bpy)2(L)]21–e2 → [RuIV(bpy)2(L)]31
(2)
thiol function cannot be ruled out. The irreversible nature
of the oxidation process in the cyclic voltammetric time-
scale has precluded its isolation and further characteriza-
tion.
The effect of the substituents (R) present in the ligand
frame (L) is observed to be much more pronounced in the

D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
2957
Fig. 4. Electronic spectrum of the oxidized complex [Ru(bpy)2L3](ClO4)2?2H2O, 1c1 in acetonitrile solution. Inset shows the electronic spectrum of 1c1
in the range 1500–800 nm.
complexes (1) can also be oxidized chemically to the same
bluish green ruthenium(III) complexes using an aqueous
ceric ammonium sulfate solution. Although all the com-
plexes can be oxidized by aqueous ceric solution, only one
trivalent complex 1c1 has been isolated in pure solid state
as dihydrated perchlorate salt. The complex 1c1 is highly
soluble in polar solvents such as acetonitrile, dimethyl-
formamide, dimethylsulfoxide and is sparingly soluble in
non-polar solvents like chloroform, dichloromethane and
benzene. The microanalytical data of the complex (1c1)
match well with the calculated values (Table 1). In the
acetonitrile solution the complex 1c1 shows 1:2 con-
ductivity (Table 1) and the complex is paramagnetic with a
magnetic moment corresponding to one unpaired electron
(m51.91 B.M.). In acetonitrile 1c1 displays two ligand-
to-metal charge-transfer (LMCT) transitions in the visible
region (Table 1, Fig. 4), as expected for the ruthenium(III)
complexes and intraligand transitions in the visible region
[56].
The EPR spectrum of 1c1 (in chloroform–toluene 1:1)
is compatible with the weak rhombic symmetry (g1 5
2.106, g2 52.093, g3 51.966; Fig. 5) [57,58]. The spec-
Fig. 5. EPR spectrum of the complex [Ru(bpy)2L3](ClO4)2?2H2O, in chloroform–toluene (1:1) glass at 77 K. Inset shows the t2 splittings.

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D. Bhattacharyya et al. / Polyhedron 18 (1999) 2951–2959
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trum was analyzed using the g-tensor theory for low-spin
d5 ions [59–63]. This yielded the values of axial distortion
(D58988 cm21) which split the t2shell into e1b and the
rhombic distortion (V50.8833 cm21) which further splits
into two non-degenerate components (Fig. 5). The value of
the orbital reduction factor, k (0.485 cm21), is also
furnished by the analysis. A pair of optical transitions n1
(1028 nm) and n2 (1186 nm) among the Kramers doublets
are predicted. One weak transition (n2) is observed in
practice at 1265 nm (Fig. 4). The other expected low-
energy transition (n1) could not be detected, possibly due
to the presence of nearby strong LMCT absorptions. In
view of the involved approximations in the theory, the
agreement between the experimentally observed n2 and the
calculated n2 value is excellent.
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4. Conclusions
We have observed the effect of the thiol-based imine
function as a third ligand in the [Ru(bpy)2] core with
respect to spectroscopic and redox properties. The pres-
ence of strong s-donor and weak p-acceptor thiol-based
ligands (L2) in the complexes (1a–1e) facilitates the
successive reversible RuII Ru
and irreversible
III
→
←
RuIII→RuIV oxidation processes. The low ruthenium(II)–
ruthenium(III) oxidation potentials of the complexes (1)
help to isolate the trivalent congeners (11) in the solid
state by both electrochemical and chemical means at room
temperature. A linear correlationship has been observed
between the formal potentials of the ruthenium(II)–
ruthenium(III) couple and the Hammett constant (s) of the
substituents (R).
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Acknowledgements
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Meyer, Inorg. Chem. 17 (1978) 2211.
Financial support received from the Department of
Science and Technology, New Delhi, India is gratefully
acknowledged. Special acknowledgement is made to the
Regional Sophisticated Instrumentation Center, RSIC, IIT
Bombay for providing NMR and EPR facilities.
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Chemists, 2nd ed., Wiley, New York, 1995.
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