Polyhedron 25 (2006) 3095–3103

www.elsevier.com/locate/poly

Synthesis, characterization, catalytic oxidation and biological activity

of ruthenium(III) Schiff base complexes derived from
3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione
Sethuraman Kannan, Rengan Ramesh *

School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu, India

Received 19 March 2006; accepted 10 May 2006

Available online 27 June 2006

Abstract

A series of air stable low spin Ru(III) complexes of the type [RuX2(EPh3)2(L)] (where X = Cl or Br; E = P or As; L = monobasic
bidentate Schiff base ligand) have been synthesized from the reaction of ruthenium(III) precursors, viz. [RuX3(EPh3)3] (where
X = Cl, E = P; X = Cl or Br, E = As) and [RuBr3(PPh3)2(CH3OH)] and Schiff bases derived from the condensation of DHA (3-acetyl-
6-methyl-2H-pyran-2,4(3H)-dione) with methylamine (HL1), cyclohexylamine (HL2) and 2-aminopyridine (HL3) in benzene under
reflux. In all these reactions, the Schiff base ligand replaces one triphenylphosphine or triphenylarsine molecule, one chloride or bromide
and one methanol from the precursors. These complexes have been characterized by elemental analyses, FT-IR, UV–Vis and EPR spec-
troscopy, together with magnetic susceptibility measurements. Elemental analyses and IR studies shows that the Schiff base ligands
behave as monobasic bidentate ligands coordinating through the oxygen atom of the deprotonated phenolic group and the nitrogen atom
of the azomethine group. The redox behavior of the complexes has been investigated by the cyclic voltammetric technique. All the com-
plexes display two quasireversible oxidations, (RuIV/RuIII) in the range 0.67–0.82 V and (RuV/RuIV) in the range 1.00–1.17 V, and an
irreversible reduction in the range 0.79 to 0.92 V. Further, the catalytic efficiency of one of the ruthenium complexes (10) was deter-
mined for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methyl-
morpholine-N-oxide(NMO) as co-oxidant. The formation of high valent RuV@O species as a catalytic intermediate is proposed for the
catalytic process. Furthermore, the in vitro toxicity of these complexes was tested against the growth of bacterial species viz., Staphylo-
coccus aureus (209p) and Escherichia coli ESS (2231).
 2006 Elsevier Ltd. All rights reserved.

Keywords: Bidentate ligand of DHA; Ruthenium(III) Schiff base complexes; Oxidation of alcohols; Antibacterial activity

1. Introduction Schiff base complexes of transition metals [6] having O

Schiff base ligands, considered as privileged ligands and
attractive due to their stability and the ease by which
modified variations can be obtained, are once again topi-
cal in connection with a diverse range of applications such
as organic synthesis [1,2], liquid crystals [3] and as molec-
ular switches in logic or memory circuits [4]. This class of
ligand is flexible in terms of both size and charge [5].
*
Corresponding author. Tel.: +91 431 2407053; fax: +0091 431
2407045/2407020.
E-mail address: ramesh_bdu@yahoo.com (R. Ramesh).
and N donor atoms have shown an exponential increase
as inorganic catalysts for various organic transformations.
Also, transition metal phosphine/arsine complexes,
especially ruthenium complexes, find application in classi-
cal catalytic processes such as hydrogenation, isomerisa-
tion, decarbonylation, reductive elimination, oxidative
addition and in making C–C bonds [7]. Unquestionably,
transition metal based catalytic systems have established
themselves as the most employed ‘work-horses’ in modern
oxidation chemistry for preparative purposes. Further,
catalytic oxidation, a challenging field of great importance
and value, has witnessed major advances since most

0277-5387/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2006.05.042
3096 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103
synthetic sequences incorporate an oxidation step in one
form or another [8]. Oxidation of primary and secondary
alcohols to aldehydes and ketones respectively, is a very
fundamental accomplishment in organic synthesis. The
transition metal-catalyzed oxidation of alcohols is of cur-
rent interest, and various metal compounds and oxidant
systems have been reported [9]. Among the second row
transition metal ions, ruthenium mediated oxidations are
finding application due to the unique properties of this
extremely versatile transition metal, whose oxidation state
can vary from II to +VIII [10]. Of mechanistic relevance
is the fact that different oxygen activated species formed
in the presence of iodosylbenzene, sodium hypochlorite,
hydrogen peroxide, t-BuOOH and N-methylmorpholine-
N-oxide as oxygen sources operate in the oxygen transfer
by these catalytic oxidation systems [11]. High valent
ruthenium-oxo complexes have proven to be very suitable
in the design of redox catalysts for a variety of reasons
[12]. Sharpless et al. [13] carried out a yield oriented study
of oxidation of cholesterol, geranial, etc., catalyzed by
ruthenium complexes in the presence of N-methylmorph-
oline-N-oxide and N,N-dimethylaniline-N-oxide. Further-
more, the catalytic activities of ruthenium complexes
containing tertiary phosphine or arsine ligands are well
established [14] and these ligands modify the oxidation
chemistry of ruthenium-oxo complexes due to their vari-
ety of steric and electronic properties [15]. In addition,
new kind of chemotherapeutic Schiff bases are now
attracting the attention of biochemists [16]. Earlier work
reported that some drugs showed increased activity when
administered as metal complexes rather than as organic
compounds [17]. Chen et al. [18] have proposed that
intercalation, hydrogen bonding and p–p interactions
are some of the features implicated in the mode of action
of ruthenium complexes as antitumour and antimetastatic
agents and some compounds are in advance stages of pre-
clinical studies. Although the mechanism of the action of
antitumour-active ruthenium compounds is not fully
understood yet, it is thought that, similar to platinum
drugs [19], the chloride complexes can hydrolyze
in vivo, allowing the Ru to bind to the nucleobases of
the DNA [20].
In continuation of our research interest [21] to under-
stand the role of these simple and inexpensive N,O-donor
ligands towards ruthenium, the reaction of Schiff bases
derived from DHA with ruthenium(III) precursors con-
taining PPh3/AsPh3 has been carried out. Thus, the present
paper describes the results of the synthesis, characterization
and redox properties of hexacoordinated Ru(III) com-
plexes exhibiting a N,O ligating core with their catalytic
activity towards oxidation of alcohols in the presence of
NMO. Further, the antibacterial activity of the Schiff bases
and their ruthenium complexes were examined. The
following Schiff bases, derived from condensation of
dehydroacetic acid (DHA) with methylamine, cyclohexyl-
amine and 2-aminopyridine (Scheme 1), were used to pre-
pare the new ruthenium(III) complexes.
R
H3C
O N
Where R = -CH3; HL1 = DHA-met
= -C6H11; HL2 = DHA-chx
O OH = -C5H4N; HL3 = DHA-ampy
H3 C
Scheme 1. Structure of Schiff bases.
2. Experimental
2.1. Reagents and materials
All the reagents used were chemically pure and were
of analytical reagent grade. The solvents were dried
and distilled before use following the standard proce-
dures [22]. RuCl3 Æ 3H2O was purchased from Loba-Che-
mie Pvt. Ltd., and was used without further purification.
The reagent N-methylmorpholine-N-oxide was obtained
from Aldrich. Dehydroacetic acid (DHA) was purchased
from SRL. The supporting electrolyte tetrabutyl ammo-
nium perchlorate (TBAP) was dried in vacuum prior to
use.
2.2. Physical measurements
The carbon, hydrogen and nitrogen microanalysis con-
tent of each sample was determined at STIC, Cochin Uni-
versity of Science and Technology, Cochin, India by
analytic function testing VarioEL III CHNS elemental
analyzer. Infrared spectra were collected using KBr pellets
on a Jasco 400 Plus, FT-IR spectrophotometer in the
range 4000–400 cm1. Electronic spectra of the complexes
in chloroform were recorded on a Cary 300 Bio UV–Vis
Varian spectrophotometer. Room temperature solid-state
magnetic susceptibilities were measured using an EG
and G model 155 vibrating sample magnetometer at
IIT, Chennai. Diamagnetic corrections calculated from
Pascal’s constants [23] were used to obtain the molar
paramagnetic susceptibilities. The X-band EPR spectra
of the powdered samples were recorded on JEOL JES-
FA200 EPR spectrometer at 278 K, the field being cali-
brated with diphenylpicryl hydrazyl (DPPH, g = 2.0037)
at Pondicherry University, India. Electrochemical studies
were performed using a Princeton EG and G-PARC
model potentiostat in 0.001 M acetonitrile solutions of
[(n-C4H9)4N]ClO4 (TBAP) as supporting electrolyte under
a nitrogen atmosphere. A three-electrode cell was
employed with a platinum working electrode, a platinum
wire auxiliary electrode and an Ag/AgCl reference elec-
trode. Melting points were recorded with a Boetius
micro-heating table and are uncorrected. The precursor
ruthenium(III) complexes [RuCl3(PPh3)3] [24], [RuCl3-
(AsPh3)3] [25], [RuBr3(AsPh3)3] [26] and [RuBr3(PPh3)2-
(CH3OH)] [27] were prepared according to the literature
procedures.
 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103
2.3. Preparation of Schiff base ligands
The monobasic bidentate Schiff base ligands were pre-
pared by the condensation of dehydroacetic acid (0.21 g,
0.125 mmol) with the primary amines methylamine, cyclo-
hexylamine and 2-aminopyridine (0.038–0.124 g, 0.125
mmol) in a 1:1 molar ratio in methanol (20 cm3). The solu-
tion was heated under reflux for 3 h and then concentrated
to 5 cm3. Slow evaporation of the solvent led to the
formation of the Schiff base ligands. The product was
recrystallized from methanol and the purity was checked
by TLC.
2.4. Synthesis of ruthenium(III) complexes
All the reactions were performed under strictly anhy-
drous conditions and the complexes were prepared by
the following general procedure. To a benzene (20 cm3)
solution of [RuX3(EPh3)3] (0.124–0.157 g, 0.125 mmol)
(X = Cl, E = P; X = Cl or Br, E = As) or [RuBr3(PPh3)2-
(CH3OH)] (0.112 g, 0.125 mmol) was added the appropri-
ate Schiff bases (0.022–0.031 g, 0.125 mmol) (HL1–HL3).
The solution was allowed to heat under reflux for 7 h.
The colour of the reaction mixture gradually deepened
and the resulting solution was concentrated to ca. 3 cm3
and cooled. Light petroleum ether (60–80 C) (5 cm3)
was then added whereupon the complex separated out.
Thus obtained solid product was recrystallized from a
CH2Cl2/light petroleum ether mixture and dried in vacuo.
The purity of the complexes were checked by TLC
(yield:55–65%).
2.5. Catalytic oxidation
The catalytic activity of one of the synthesized com-
plexes [RuCl2(AsPh3)2(DHA-ampy)] (10) for the oxidation
of primary and secondary alcohols to their corresponding
aldehydes or ketones was determined in the presence of
NMO as co-oxidant. A typical reaction using the complex
as a catalyst and various activated and non-activated alco-
hols as substrates in 1:100 molar ratio is described as fol-
lows. A solution of ruthenium complex 10 (0.01 mmol) in
20 cm3 CH2Cl2 was added to the solution of the substrate
(1 mmol) and NMO (3 mmol). The solution mixture was
refluxed for an appropriate period of time, as mentioned,
and the solvent was then evaporated from the mother
liquor under reduced pressure. The solid residue was then
extracted with petroleum ether (60–80 C) (20 cm3) and
the products were analyzed and quantified by GC. In case
of benzhydrol and benzoin, the products benzophenone
and benzil were isolated and confirmed by melting point,
IR and 1H NMR.
2.6. Antibacterial activity
The in vitro antibacterial screening effects of the investi-
gated compounds were tested against the bacteria Staphylo-
3097
coccus aureus (209p) and Escherichia coli ESS (2231) by the
well diffusion method using agar nutrient as the medium at
37 C for 18 h. The stock solutions of the Schiff bases and
the complexes were prepared in 10% DMSO in methanol
and were stored dry at room temperature. In a typical pro-
cedure [28] a well was made on the agar medium inoculated
with microorganisms. The well was then filled with the test
solution using a micropipette and the plates were incubated
at 35 C for 24 h for bacteria. During this period, the test
solutions diffused and the growth of the inoculated micro-
organisms was affected. The inhibition zone developed on
the plate was measured and the data is summarized in
Table 6. Ampicillin was used as the control.
3. Results and discussions
The reactions of [RuX3(EPh3)3] (X = Cl, E = P; X = Cl
or Br, E = As) or [RuBr3(PPh3)2(CH3OH)] with Schiff base
ligands (HL1–HL3) in a 1:1 molar ratio in dry benzene
afforded new hexacoordinated low spin ruthenium(III)
Schiff base complexes. The reaction proceeds as shown in
Scheme 2. The proposed molecular formulae for all the
complexes are in good agreement with the stoichiometries
concluded from their analytical data (Table 1). In all these
reactions, the Schiff bases behave as monobasic bidentate
ligands replacing one triphenylphosphine or triphenylar-
sine molecule, one chloride or bromide and one methanol
ligand from the precursors. All the complexes are air-
stable, non-hygroscopic in nature, insoluble in water and
highly soluble in common solvents such as dichloro-
methane, acetonitrile, chloroform and DMSO, producing
intense dark color solutions.
R
H3C
[Ru X3(EPh3)3] O N
E = P; X = Cl
E = As; X = Cl or Br O OH
(or)
H3C
[RuBr3(PPh3)2(CH3OH)]
R= - CH3 , - C6H11 , - C5H4N
Benzene
1:1
Reflux/7 h
R
H3C EPh3
O N X
Ru
O O X
EPh3
H3C
X = Cl or Br ; E = P or As
R= - CH3 , - C6H11 , - C5H4N
Scheme 2. Structure of Ru(III) Schiff base complexes.
3098 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103

Table 1
Analytical data of ruthenium(III) Schiff base complexes
S. No. Complexes Empirical formula Colour m.p. (C) Elemental analysis
Found(calculated) (%)
C H N
1 [RuCl2(PPh3)2(DHA-met)] C45H40NO3Cl2P2Ru brown 160 61.23(61.64) 4.43(4.56) 1.79(1.59)
2 [RuCl2(AsPh3)2(DHA-met)] C45H40NO3Cl2As2Ru brown 154 55.86(56.01) 3.98(4.15) 1.25(1.45)
3 [RuBr2(AsPh3)2(DHA-met)] C45H40NO3Br2As2Ru brown 176 50.98(51.28) 3.46(3.79) 1.19(1.33)
4 [RuBr2(PPh3)2(DHA-met)] C45H40NO3Br2P2Ru brown 172 55.65(55.95) 3.88(4.14) 1.20(1.45)
5 [RuCl2(PPh3)2(DHA-chx)] C50H48NO3Cl2P2Ru brown 160 63.19(63.55) 4.82(5.08) 1.24(1.48)
6 [RuCl2(AsPh3)2(DHA-chx)] C50H48NO3Cl2As2Ru brown 172 57.96(58.13) 4.35(4.65) 1.19(1.35)
7 [RuBr2(AsPh3)2(DHA-chx)] C50H48NO3Br2As2Ru brown 175 53.22(53.52) 4.02(4.28) 1.04(1.25)
8 [RuBr2(PPh3)2(DHA-chx)] C50H48NO3Br2P2Ru brown 193 57.89(58.08) 4.45(4.64) 1.08(1.35)
9 [RuCl2(PPh3)2(DHA-ampy)] C49H41N2O3Cl2P2Ru brown 198 62.24(62.57) 4.16(4.36) 2.69(2.97)
10 [RuCl2(AsPh3)2(DHA-ampy)] C49H41N2O3Cl2As2Ru brown 179 56.89(57.20) 3.72(3.99) 2.48(2.72)
11 [RuBr2(AsPh3)2(DHA-ampy)] C49H41N2O3Br2As2Ru brown 178 52.26(52.66) 3.41(3.67) 2.22(2.50)
12 [RuBr2(PPh3)2(DHA-ampy)] C49H41N2O3Br2P2Ru brown 168 56.94(57.16) 3.72(3.98) 2.34(2.72)

3.1. Spectroscopic characterization complexes m(C–O) = 1273–1276 cm1 [30]. This fact is
further supported by the disappearance of the m(OH) band
The IR bands for the metal complexes derived from in the range 3415–3434 cm1 for all the complexes, indicat-
Schiff bases of DHA, which are most useful in attempting ing the subsequent deprotonation of the phenolic proton
to determine the mode of coordination, are listed in Table prior to coordination. Bands in the 510–550 and 450–
2. The IR spectra of the free Schiff base ligands show a 475 cm1 regions are ascribed to the formation of M–O
strong band in the region 1640–1659 cm1 that is charac- and M–N bonds, respectively [31] which further supports
teristic of the azomethine group. Coordination of the Schiff the coordination of the azomethine nitrogen and the phe-
bases to the metal through the nitrogen atom is expected to nolic oxygen. The bands observed in the range 1719–
reduce the electron density in the azomethine frequency. 1728 cm1 of the ligands are due to the lactone carbonyl
The band due to azomethine nitrogen m(C@N) shows a mod- group, which remain unchanged after complexation indi-
est decrease in the stretching frequency for the complexes cating that they do not participate in bond formation with
and is shifted to lower frequencies, appearing around the metal ion. Further, the ruthenium(III) Schiff base com-
1631–1651 cm1, which indicates the coordination of the plexes show strong vibrations near 520, 695, 740, 1445 and
azomethine nitrogen [21a,29]. Also, there is an upward 1532 cm1, which are attributable to the triphenylphos-
shift in the stretching frequency of phenolic oxygen in the phine or triphenylarsine fragments [32].
The electronic spectra of the ruthenium(III) complexes
were recorded in chloroform in the range 800–200 nm.
Table 2 Most of the complexes showed two to three bands in the
IR and electronic spectral data of ruthenium(III) Schiff base complexesc region 812–241 nm, and are listed in Table 2. The ground
Complexes m(C@N) m(C–O) kmax (e) state of ruthenium(III) in an octahedral environment is
2
1 1651 1270 790a(557), 513b(1695), 301(10 391), T2g, arising from the t52g configuration, and the first excited
249(20 326) doublet levels in the order of increasing energy are 2A2g and
812a(511), 515b(2053), 303(12 730), 2
2 1649 1272 T1g, arising from the t42g e1g configuration. Hence, two
247(21 730)
bands corresponding to 2T2g ! 2A2g and 2T2g ! 2T1g are
3 1645 1270 563b(1325), 310(19 788), 265(22 134)
4 1642 1274 520b(2130), 243(32 208) possible. The absorption bands around 812–704 and 586–
5 1646 1272 794a(640), 522b(2166), 311(23 238) 513 nm are assigned to d–d (e = 511–556 dm3/mol/cm)
6 1649 1270 754a(640), 562b(2684), 394(12 342), and charge transfer (LMCT) (e = 1639–1696 dm3/mol/
252(18 234) cm) transitions respectively. In most ruthenium(III) Schiff
7 1647 1275 554b(1675), 341(12 039), 318(19 517)
8 1650 1272 535b(1814), 315(12 266), 245(21 976)
base chelates, charge transfer bands of the type Lpy ! T2g
9 1631 1273 738a(658), 558b(1974), 363(19 181), are prominent in the low energy region, which obscures the
301(23 257) weaker bands due to d–d transitions [21a]. It is therefore
10 1635 1275 704a(556), 568b(1668), 364(18 507) difficult to assign conclusively the bands of the ruthe-
11 1632 1276 739a(479), 586b(1639), 320(16 765), nium(III) complexes that appear in the visible region.
241(21 345)
12 1633 1275 711a(587), 573b(2154), 367(14 152),
However, the extinction coefficients for the bands 812–
308(19 894) 704 nm are found to be low compared to that of the charge
a 2
T2g ! 2A2g.
transfer bands. Hence, the bands around 812–704 nm have
b
Charge transfer (LMCT). been assigned to the 2T2g ! 2A2g transition, which is in con-
c
Where m is in cm1, kmax is in nm, e is in dm3 mol1 cm1. formity with the assignment made for similar octahedral
 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103 3099

ruthenium(III) complexes [33]. The spectral profiles below

400 nm are very similar and are ligand centered transitions.
These bands have been designated as p–p* and n–p* transi-
tions of non-bonding electrons present on the nitrogen of
the azomethine group in the Schiff base complexes [21a].
The pattern of the electronic spectra of all the ruthe-
nium(III) Schiff base complexes indicates the presence of
an octahedral environment around the ruthenium(III) ion.

3.2. Magnetic moments and EPR spectra

The room temperature magnetic susceptibility measure-

ments for the complexes lie in the range 1.79–1.92 BM,
which indicates that these complexes are one electron para-
magnetic, suggesting a low spin t52g (S = 1/2) configuration
around the ruthenium(III) ion in an octahedral
environment.
The room temperature solid-state EPR spectra of all the
complexes were recorded at X-band frequencies. The ‘g’ Fig. 1. EPR spectrum of [RuCl2(PPh3)2(DHA-met)].
values are given in Table 3 and a representative spectrum
is shown in Fig. 1. The low spin d5 configuration is a good
probe of the molecular structure and bonding since the
observed ‘g’ values are very sensitive to small changes in
the structure and to metal–ligand covalency. The EPR
spectra of all the complexes exhibit two different ‘g’ values
(gx = gy 6¼ gz) with g^ = 2.03–2.39 and gi = 1.99–1.89,
characteristic of an axially symmetric system. The presence
of two different ‘g’ values indicate a tetragonal distortion in
the complexes [21a,34]. Overall the positions of lines and
nature of the EPR spectra of the complexes are character-
istic of low spin ruthenium(III) octahedral complexes.

3.3. Electrochemistry of the complexes

The redox properties of all the complexes were investi-

gated in dichloromethane solution with tetrabutyl ammo- Fig. 2. Cyclic voltammogram of [RuBr2(AsPh3)2(DHA-ampy)].
nium perchlorate (TBAP) as the supporting electrolyte by
cyclic voltammetry and the redox potentials are expressed
with reference to Ag/AgCl. A representative cyclic voltam- data are presented in Table 4. All the complexes displayed
mogram of complex 11 is shown in Fig. 2 and voltammetric two quasi-reversible oxidation couples RuIII/RuIV at
E1/2 = 0.67–0.82 V with a peak-to-peak separation DEP =
100–150 mV and RuIV/RuV with E1/2 = 1.00–1.17 V with
Table 3 DEP = 150–210 mV, with respect to Ag/AgCl, which do
EPR data of ruthenium(III) Schiff base complexes not change with a change in scan rates, supporting revers-
Complexes gx gy gz Ægæ* ibility [35]. The oxidations observed are quasi-reversible in
nature, characterized by a rather large peak-to-peak sepa-
1 2.25 2.25 1.99 2.16
2 2.23 2.23 1.98 2.14 ration (DEp), and the cathodic peak current (ipc) is less than
3 2.34 2.34 1.89 2.19 the anodic peak current (ipa). Further, all the complexes
4 2.33 2.33 1.94 2.20 exhibit an irreversible reduction in the range 0.79 to
5 2.14 2.14 1.96 2.08 0.92 V. The reason for the irreversibility observed for
6 2.24 2.24 1.95 2.14
the reductive response of all the complexes may be due to
7 2.32 2.32 1.93 2.19
8 2.39 2.39 1.95 2.24 a short lived reduced state of the metal ion [36] or due to
9 2.03 2.03 1.98 2.01 oxidative degradation of the ligands [37]. In these redox
10 2.27 2.27 1.94 2.16 couples, electrons are gained or lost from the dp levels orbi-
11 2.28 2.28 1.94 2.16 tal of the coordinated metal [38]. There is not much varia-
12 2.26 2.26 1.94 2.16
tion due to replacement of chlorides by bromides and
hgi ¼ ½1=3g2x þ 1=3g2y þ 1=3g2z 1=2 . triphenylphosphine by triphenylarsine. Hence, it is inferred
3100 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103

Table 4
Electrochemical data of ruthenium(III) Schiff base complexes
Complexes RuIII/RuIV RuIV/RuV RuIII/RuII
Epa Epc DEP (mV) E1/2 (V) Epa Epc DEP (mV) E1/2 (V) Epc
1 0.87 0.73 140 0.80 1.23 1.05 180 1.14 0.86
2 0.84 0.74 100 0.79 1.24 1.03 210 1.13 0.87
3 0.85 0.70 150 0.77 1.23 1.03 200 1.13 0.88
4 0.84 0.74 100 0.79 1.19 1.01 180 1.10 0.79
5 0.86 0.74 120 0.80 1.23 1.07 160 1.15 0.92
6 0.72 0.62 100 0.67 1.08 0.93 150 1.00 0.89
7 0.83 0.72 110 0.77 1.23 1.04 190 1.13 0.81
8 0.87 0.75 120 0.81 1.25 1.05 200 1.15 0.85
9 0.90 0.75 150 0.82 1.13 0.97 160 1.05 0.88
10 0.85 0.72 130 0.78 1.26 1.08 180 1.17 0.80
11 0.84 0.73 110 0.79 1.22 1.05 170 1.13 0.85
12 0.87 0.76 110 0.81 1.21 1.03 180 1.12 0.87
Supporting electrolyte, NBu4ClO4 (0.005 M); complex, 0.001 M; solvent, CH3CN; DEp = Epa  Epc where Epa and Epc are anodic and cathodic potentials
respectively; E1/2 = 0.5(Epa + Epc); scan rate: 100 mV s1.

from the electrochemical data that the present ligand Table 5

system is ideally suitable for stabilizing the higher oxida- Catalytic oxidation of alcohols by [RuCl2(AsPh3)2(DHA-ampy)] /NMO
tion state of ruthenium. Entry Substrates Products Time (h) Yieldb (%)
1 OH
CHO 3 88
3.4. Catalytic activity of the complexes
2 OH
CHO 3 96
Catalytic oxidation of primary and secondary alcohols
by one of the synthesized ruthenium(III) Schiff base com- 3 O O 3 52a
plexes was carried out in CH2Cl2 in the presence of OH O

NMO and the by-product water was removed using molec- 4 OH O 7 99

ular sieves. The results are summarized in Table 5. The cat-
alytic reaction was carried out under a set of conditions OH O
5 7 90
(see experimental for reaction conditions) and a series of
blank or control experiments suggest that none of
RuCl3 Æ 3H2O, Ru(III) precursors or DHA-ampy, NMO 6 OH O
8 99
alone or as a mixture causes these transformations under
identical reaction conditions. This ascertained the necessity 7 OH O
8 98
of the ruthenium(III) complex to observe the ensuing
catalytic organic transformations. Complex 10 oxidizes 8 OH O
3 65a
primary alcohols to the corresponding aldehydes and
secondary alcohols to ketones with high yield. 9 OH O
4 63

OH [RuCl2(AsPh 3)2(DHAampy)]
O
OH O
0.01mmol
H2O 10 4 88
R R' NMO/CH2Cl2 R R' CH 3O
CH3O
reflux
OH
11 O 7 84
R, R' = alkyl (or) aryl
OH O
12 7 92
The aldehydes or ketones formed after reflux for the
time mentioned was determined by GC with authentic sam- Substrate (1 mmol); NMO (3 mmol); complex (0.01 mmol); solvent –
ples. Results of the present investigation suggest that the dichloromethane.
a
complexes are able to react efficiently with NMO to yield Isolated yield, characterized by melting point, IR and 1H NMR.
b
a high valent ruthenium-oxo species [39,40], capable of Yield determined by GC and comparing with authentic samples.
oxygen transfer to alcohols. This was further supported
by changes that occur on addition of NMO to a dichloro- support in favor of the formation of such species is identi-
methane solution of the ruthenium(III) complexes. The fied from the IR spectrum of the solid mass (obtained by
appearance of the peak at 380 nm is attributed to the for- evaporation of the resultant solution to dryness), which
mation of RuV@O species, which is in conformity with shows a band at 860 cm1, characteristic of ruthenium(V)-
other ruthenium(V)-oxo complexes [40–42]. Further, oxo species [11d,40,41a] (see Scheme 3).
 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103 3101

O and Gram ve (E. coli ESS 2231). The test solutions were
H2O Ru III
NMO prepared in dimethyl sulfoxide and the results are summa-
R R'
rized in Table 6. Blank experiments with RuCl3 Æ 3H2O and
the Ru(III) precursors were carried out under identical
experimental conditions and show the inability of these
OH complexes to inhibit the bacterial growth. The effectiveness
RuV = O NM
of an antimicrobial agent in sensitivity is based on the
R R'
zones of inhibition. The diameter of the zone is measured
R, R' = alkyl(or)aryl
to the nearest millimeter (mm).
Scheme 3. Proposed catalytic cycle for the oxidation of alcohols by the The obtained results indicate that the complexes (ruthe-
Ru(III) Schiff base complex. nium chelates) are more toxic than the free ligands against
same microbes under identical experimental conditions.
The oxidation of benzyl alcohol to benzaldehyde This would suggest that the chelation could facilitate the
resulted in 89% conversion. An important characteristic ability of a complex to cross a cell membrane [43] and
of the ruthenium/NMO system results in the selective can be explained by Tweedy’s chelation theory [44]. Chela-
oxidation at the alcoholic group of unsaturated cinnamyl tion considerably reduces the polarity of the metal ion
alcohol to cinnamaldehyde, tolerating the other reactive because of partial sharing of its positive charge with donor
functional group (double bond). In case of benzoin and groups and possible p-electron delocalization over the
benzhydrol, the oxidized products, benzil and benzophe- whole chelate ring. Such a chelation could enhance the
none respectively, were isolated and characterized by lipophilic character of the central metal atom, which subse-
melting point, IR and 1H NMR. quently favors its permeation through the lipid layers of the
Allylic and benzylic alcohols are oxidized with maxi- cell membrane [45] and blocking the metal binding sites on
mum selectivity to aldehydes with, importantly, no further enzymes of microorganisms. The different compounds
oxidation to the corresponding carboxylic acids. Unacti- exhibit microbial activity with small variations against
vated secondary alcohols such as 2-butanol and 2-pentanol the bacterial species and this difference in activity could
were also effectively oxidized into their corresponding be attributed to the impermeability of the cell of the
ketones, ethyl methyl ketone and ethyl propyl ketone with microbes which, in the case of Gram +ve is single layered
84% and 92% conversion respectively. Also, activated sec- and in the case of Gram ve is a multilayered structure
ondary alcohols such as 1-phenyl ethanol and 4-methoxy- [46] or differences in the ribosomes of the microbial cells.
1-phenyl ethanol undergo significant oxidation to give their The observed results seem to conclude that the present
corresponding ketones with high selectivities of 63% and ruthenium(III) chelates possess more cytotoxicity than
88% conversion respectively. The higher conversion in the the free Schiff base ligands. Further, it has been noted that
case of 4-methoxy-1-phenyl ethanol, when compared to these complexes show better antibacterial activity when
1-phenyl ethanol, is due to the presence of the electron- compared to other metal complexes against the microbes
withdrawing methoxy (OCH3) group, which increases the S. aureus and E. coli [47]. Though complexes of this type
reactivity by destabilizing the ruthenium-oxo intermediate
making it a more reactive oxidant [8]. Interestingly, the Table 6
complex efficiently catalyses the oxidation of five, six, seven Antibacterial activities of ruthenium(III) Schiff base complexes
and eight membered cyclic alcohols to the corresponding Sl. No. Complexes Diameter of inhibition zone
ketones with conversions >90% respectively. (mm)
It has been observed that these ruthenium(III) Schiff base S. aureus E. coli ESS
complexes have better catalytic efficiency in the case of oxi- (209p) (100 ll) (2331) (100 ll)
dation of benzyl alcohol, cinnamyl alcohol and cyclohexanol 1 DHA-met – –
when compared to the earlier reports [11d,40–42], on similar 2 [RuCl2(PPh3)2(DHA-met)] 12 13
ruthenium complexes as catalysts in the presence of NMO/ 3 [RuCl2(AsPh3)2(DHA-met)] 13 13
t-BuOOH. Hence, it is relevant from the cyclic voltammetric 4 [RuBr2(AsPh3)2(DHA-met)] 11 12
5 [RuBr2(PPh3)2(DHA-met)] 10 10
data that the oxidation is likely to occur via higher ruthe-
6 DHA-chx – –
nium oxidation states, which are easily accessible through 7 [RuCl2(PPh3)2(DHA-chx)] 14 9
chemical oxidation with the co-oxidant NMO [39,42]. 8 [RuCl2(AsPh3)2(DHA-chx)] 11 11
9 [RuBr2(AsPh3)2(DHA-chx)] 10 8
3.5. Antimicrobial studies 10 [RuBr2(PPh3)2(DHA-chx)] 12 10
11 DHA-ampy – –
12 [RuCl2(PPh3)2(DHA-ampy)] 11 10
The Schiff base ligands and ruthenium(III) complexes 13 [RuCl2(AsPh3)2(DHA-ampy)] 16 15
were screened in vitro for their microbial activity against 14 [RuBr2(AsPh3)2(DHA-ampy)] 15 11
two human pathogenic bacterial species using the well dif- 15 [RuBr2(PPh3)2(DHA-ampy)] 11 13
fusion method. These compounds were found to exhibit – No inhibition; standard; solvent, DMSO (no inhibitory against the
considerable activity against Gram +ve (S. aureus 209p) microorganisms).
3102 S. Kannan, R. Ramesh / Polyhedron 25 (2006) 3095–3103
were found to have potential antibacterial activity against
the bacterial microbes, they could not reach the effective-
ness of the conventional bacterial control Ampicillin.
4. Conclusion
In summary, we have synthesized and characterized a
series of new ruthenium(III) Schiff base complexes incorpo-
rating triphenylphosphine/triphenylarsine and chloride/
bromide ligands. One of the complexes has been tested as
a new and efficient catalyst for the oxidation of both pri-
mary and secondary alcohols to the corresponding car-
bonyl compounds with excellent yields in the presence of
N-methylmorpholine-N-oxide. Further, the possible expla-
nations for the mode of action of these complexes against
two different microbes are described.
Acknowledgement
We express our sincere thanks to Professor P. Sambas-
iva Rao, Department of Chemistry, Pondicherry Univer-
sity for providing the EPR facility.
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