Spectrochimica Acta Part A 68 (2007) 50–54

Synthesis, spectral, catalytic and antimicrobial studies

of PPh3/AsPh3 complexes of Ru(II) with dibasic
tridentate O, N, S donor ligands
K.P. Balasubramanian a , R. Karvembu b,∗ , R. Prabhakaran c ,
V. Chinnusamy a,∗ , K. Natarajan c
a Department of Chemistry, Sri Ramakrishna Mission Vidyalaya College of Arts and Science,
Coimbatore 641 020, India
b Department of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India
c Department of Chemistry, Bharathiar University, Coimbatore 641 046, India

Received 30 September 2006; accepted 31 October 2006

Abstract
Complexes of the type [Ru(CO)(EPh3 )(B)(L)] (E = P or As; B = PPh3 , AsPh3 , py or pip; L = dianion of the Schiff bases derived from thiosemicar-
bazone with acetoacetanilide, acetoacet-o-toluidide and o-chloro acetoacetanilide) have been synthesized from the reactions of equimolar amounts
of [RuHCl(CO)(EPh3 )2 (B)] and Schiff bases in benzene. The new complexes have been characterized by analytical and spectral (IR, electronic,
NMR) data. The arrangement of PPh3 groups around ruthenium metal was determined from 31 P NMR spectra. An octahedral structure has been
assigned for all the new complexes. All the complexes exhibited catalytic activity for the oxidation of benzyl alcohol and cyclohexanol in presence
of N-methylmorpholine-N-oxide as co-oxidant. The complexes also exhibited antibacterial activity against E. coli, Aeromonas hydrophilla and
Salmonella typhi. The activity was compared with standard streptomycin.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Thiosemicarbazone; Ruthenium(II); Catalytic oxidation; Antibacterial activity

1. Introduction
Mixed ligand complexes of transition metals containing lig-
ands with N, S or N, S, O donors are known to exhibit interesting
stereochemical, electrochemical and electronic properties [1,2].
Derivatives of semicarbazones and thiosemicarbazones are
amongst the most widely studied nitrogen and oxygen/sulphur
donor ligands [3,4]. Particularly thiosemicarbazones have
emerged as an important class of sulphur donor ligands for
transition metal ions in the last two decades. The real impe-
tus towards developing their coordination chemistry was their
physicochemical properties and significant biological activities
[5,6]. The chemistry of ruthenium is currently receiving a lot
of attention, primarily because of the fascinating electron trans-
fer and energy transfer properties displayed by the complexes of
this metal [7]. Ruthenium offers a wide range of oxidation states
∗ Corresponding authors. Tel.: +91 4312501801; fax: +91 4312500133.
E-mail address: kar@nitt.edu (R. Karvembu).
and the reactivity of the ruthenium complexes depend on the sta-
bility and interconvertibility of these oxidation states, which in
turn depend on the nature of the ligands bound to the metal.
Complexation of ruthenium by ligands of different types has
thus been of particular interest. Moreover, transition metal com-
plexes of tridentate Schiff base ligands have been successfully
used in several catalytic reactions [8,9].
2. Experimental
2.1. Reagents and materials
All the reagents used were of analar or chemically pure
grade. Solvents were purified and dried according to stan-
dard procedures. RuCl3 ·3H2 O purchased from Loba Chemie
was used without further purification. The starting com-
plexes [RuHCl(CO)(PPh3 )3 ] [10], [RuHCl(CO)(B)(PPh3 )2 ]
(B = pyridine or piperidine) [11] and [RuHCl(CO)(AsPh3 )3 ]
[12] and the ligands [13] were prepared according to the litera-

1386-1425/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2006.10.049
 K.P. Balasubramanian et al. / Spectrochimica Acta Part A 68 (2007) 50–54 51

ture procedures. Catalytic oxidation of alcohols and antibacterial

studies were carried out according to our earlier procedures
[13,14].

2.2. Physical measurements

The analysis of C, H and N were performed at the Cen-

tral Drug Research Institute, Lucknow, India. FT-IR spectra of
the complexes were recorded as KBr pellets on a Shimadzu
8000 FT-IR spectrophotometer in the range 4000–400 cm−1 .The
electronic spectra were recorded in CH2 Cl2 solution with a
Systronics 119 spectrometer in the range 800–200 nm. 1 H
and 31 P NMR spectra were recorded on Bruker 400 MHz
or Varian FX 90 Q instrument using TMS and orthophos-
phoric acid as references respectively. The antibacterial
studies were carried out at the Department of Environ-
mental Sciences, Bharathiar University, Coimbatore. Melting
points were recorded with a Raaga heating table and are
uncorrected.
2.3. Recommended procedures
2.3.1. Synthesis of new Ru(II) complexes
To a solution of [RuHCl(CO)(PPh3 )3 ], [RuHCl(CO)-
(PPh3 )2 (py)], [RuHCl(CO)(PPh3 )2 (pip)] or [RuHCl(CO)-
(AsPh3 )3 ] (0.1 g, 0.08–0.1 mmol) in benzene (20 cm3 ) the
respective Schiff base ligands (0.03–0.08 g, 0.08–0.1 mmol)
were added. The mixture was then heated under reflux for 6 h.
The resulting solution was concentrated to ca. 3 cm3 and the
product was separated by the addition of the small amount of
light petroleum (60–80 ◦ C). It was filtered and recrystallised
from CH2 Cl2 /light petroleum (60–80 ◦ C) and dried in vacuum
(yields = 70–83%).
3. Results and discussion
Light and air stable ruthenium(II) complexes of the general
formula [Ru(CO)(EPh3 )(B)(L)] [E = P or As; B = PPh3 , AsPh3 ,
pyridine (py) or piperidine (pip); L = tridentate Schiff base
Fig. 1. Structure of Schiff base ligands.
anion] have been prepared by reacting [RuHCl(CO)(EPh3 )2 (B)]
with the respective Schiff bases in a 1:1 molar ratio in benzene
(Fig. 1).
 
RuHCl(CO)(EPh3 )2 (B) + H2 L
benzene
−→ [Ru(CO)(EPh3 )(B)(L)] + HCl + EPh3 + H2
reflux, 6 h
All the complexes are green in colour. The analytical data
obtained for the new complexes (Table 1) agree very well with
the proposed molecular formulae. In all of the above reactions,
the Schiff bases behave as binegative tridentate ligands. The new
products obtained from the reactions of [RuHCl(CO)(PPh3 )3 ]
with Schiff base ligands contained two triphenylphosphine
on ruthenium ion, whereas the corresponding reactions of
[RuHCl(CO)(py)(PPh3 )2 ] or [RuHCl(CO)(pip)(PPh3 )2 ] with
Schiff base ligands yielded new complexes with only one triph-
enylphosphine ligand on ruthenium ion. These observations do
indicate a more labile nature of Ru P bond compared to the
Ru N bond of the heterocyclic nitrogen bases to the ruthe-
nium ion in these complexes. The difference in the strength of
Ru P and Ru N bonds may be explained as due to their bet-

Table 1
Analytical data of new Ru(II) complexes
Complex mp (◦ C) Yield (%) Found (calculated) (%)

C H N

[Ru(CO)(PPh3 )2 (AAT)] 180 83 63.84 (63.85) 4.75 (4.76) 6.19 (6.20)

[Ru(CO)(PPh3 )2 (ATT)] 185 81 64.17 (64.19) 4.90 (4.91) 6.10 (6.11)
[Ru(CO)(PPh3 )2 (CAT)] 178 85 61.83 (61.86) 4.50 (4.51) 6.00 (6.01)
[Ru(CO)(AsPh3 )2 (AAT)] 160 74 63.89 (63.90) 4.14 (4.34) 5.67 (5.65)
[Ru(CO)(AsPh3 )2 (ATT)] 168 75 61.83 (61.56) 3.91 (4.48) 5.56 (5.57)
[Ru(CO)(AsPh3 )2 (CAT)] 165 83 56.45 (56.47) 4.10 (4.11) 5.47 (5.49)
[Ru(CO)(PPh3 )(py)(AAT)] 172 78 55.98 (56.00) 4.41 (4.40) 9.32 (9.33)
[Ru(CO)(PPh3 )(py)(ATT)] 174 82 56.53 (56.54) 4.57 (4.58) 9.17 (9.16)
[Ru(CO)(PPh3 )(py)(CAT)] 172 85 53.83 (53.84) 4.11 (4.10) 8.96 (8.97)
[Ru(CO)(PPh3 )(pip)(AAT)] 181 73 53.49 (53.50) 4.70 (4.71) 8.92 (8.91)
[Ru(CO)(PPh3 )(pip)(ATT)] 179 70 54.05 (55.06) 4.87 (4.88) 8.90 (8.91)
[Ru(CO)(PPh3 )(pip)(CAT)] 168 75 51.52 (51.53) 4.40 (4.41) 3.63 (3.62)
52 K.P. Balasubramanian et al. / Spectrochimica Acta Part A 68 (2007) 50–54

Fig. 2. Tautomerism in ligands.

ter ␴ donating ability of the nitrogen bases compared to that of
triphenylphosphine.
3.1. Spectroscopic studies
The FT-IR spectra of the free ligands were compared with
that of the new complexes in order to confirm the coordina-
tion of ligand to the ruthenium metal. The ligands used in the
present study can exhibit both keto–enol and thione–thiol tau-
tomerism (Fig. 2). The IR spectrum of free ligands display two
bands around 3450 and 3300 cm−1 due to νas and νsym of ter-
minal NH2 group [15]. These bands remain unaltered in the
corresponding metal complexes indicating the non-involvement
of this group on complexation. The absorption due to νC N of
the free ligand appearing in the 1620 cm−1 region undergoes
a negative shift by 5–25 cm−1 in the spectra of the complexes
indicating the coordination of azomethine nitrogen to the metal
[14]. A strong band which appeared in the spectra of the ligands
around 1650 cm−1 due to νC O completely disappeared and a
new band was observed around 1620 cm−1 . This may due to
the enolisation and subsequent coordination through the depro-
tonated oxygen atom of the CH2 C O group [13]. The band
due to νC S appeared around 830 cm−1 in the free ligands has
disappeared on complexation and a new band appeared around
720–750 cm−1 . These observations may be attributed to thio
enolisation of the NH C S group and subsequent coordina-
tion through the deprotonated sulphur [16]. In all the carbonyl
complexes, the band due to terminal C O group appeared at
1900–1944 cm−1 . The absorption due to coordinated pyridine
and piperidine appeared in the region 1000–1035 cm−1 . In addi-
tion to the above, the characteristic bands due to PPh3 or AsPh3
were also present in the expected region [17]. From the IR spec-
tral data, it is inferred that the Schiff bases behave as dibasic
tridentate ligands and the coordination sites are ␤-nitrogen, thi-
olatosulphur and oxygen after deprotonation. The possibility of
␣-nitrogen coordination is ruled out because of considerable
strain.
All the complexes are diamagnetic indicating the presence
of ruthenium in +2 oxidation state in all the complexes. In the
electronic spectra (Table 2) of all the complexes in CH2 Cl2 ,
three to four bands are appeared in the region 620–245 nm. The
bands in the region 620–570 nm are assigned to the transition
1 A → 3 T and the bands around 370–400 nm are due to 1 A
1g 1g 1g
→ 3 T2g transition. The other bands in the region 320–245 nm
are probably due to charge transfer transitions (t2g → ␲* ). The
nature of the electronic spectra are similar to those observed
for other octahedral ruthenium(II) complexes [18].
The ligand to metal bonding is further supported by 1 H
NMR spectra (Table 3). All the complexes showed signals in the
7.0–7.99 ppm range due to the phenyl protons of Schiff base and
PPh3 /AsPh3 . The azomethine proton signals in the complexes
lie in the 8.0–8.65 ppm range. The peak due to the azomethine
showed a high field shift compared to the free Schiff base after
complexation with the metal ion indicating coordination through
the azomethine nitrogen atom [19]. Further, the signal for methy-
lene protons appear as a singlet in the region 3.16–3.19 ppm [20].
The signal for terminal NH2 protons appears as a singlet in the
region 4.45–4.57 ppm. The spectra of [Ru(CO)(AsPh3 )2 (ATT)]
and [Ru(CO)(PPh3 )(py)(ATT)] showed a singlet at 1.6 ppm for
the protons of methyl group attached in the phenyl ring.
The 31 P NMR spectra for three of the complexes were
recorded in order to confirm the presence of PPh3 groups and to

Table 2
IR and electronic spectral data of Ru(II) complexes
Complex νC S νC N νN H νN C N λmax (nm)

[Ru(CO)(PPh3 )2 (AAT)] 692 1596 3100 1070 650, 400, 260

[Ru(CO)(PPh3 )2 (ATT)] 692 1598 3119 1080 370, 300, 260
[Ru(CO)(PPh3 )2 (CAT)] 692 1591 3120 1075 651, 392, 265
[Ru(CO)(AsPh3 )2 (AAT)] 692 1596 3120 1070 400, 295, 255
[Ru(CO)(AsPh3 )2 (ATT)] 692 1596 3120 1070 390, 315, 255
[Ru(CO)(AsPh3 )2 (CAT)] 692 1594 3120 1075 400, 325, 263
[Ru(CO)(PPh3 )(py)(AAT)] 692 1593 3127 1073 581, 385
[Ru(CO)(PPh3 )(py)(ATT)] 692 1597 3120 1073 585, 390
[Ru(CO)(PPh3 )(py)(CAT)] 692 1595 3120 1070 580, 436, 315
[Ru(CO)(PPh3 )(pip)(AAT)] 692 1596 3120 1080 435, 320
[Ru(CO)(PPh3 )(pip)(ATT)] 692 1591 3118 1074 575, 450, 265
[Ru(CO)(PPh3 )(pip)(CAT)] 692 1598 3117 1073 620, 400, 320

ν in cm−1 ; λ in nm.
 K.P. Balasubramanian et al. / Spectrochimica Acta Part A 68 (2007) 50–54 53

Table 3
1H and 31 P NMR spectral data of Ru(II) complexes
Complex 1H NMR 31 P NMR

[Ru(CO)(PPh3 )2 (AAT)] 7.0–7.90 (m, aromatic), 8.5 (s, CH N), 3.17 (s, CH2 ), 4.57 (s, NH2 ) 28.65
[Ru(CO)(PPh3 )2 (CAT)] 7.01–7.86 (m, aromatic), 8.1 (s, CH N), 3.19 (s, CH2 ), 4.58 (s, NH2 ) 28.72
[Ru(CO)(AsPh3 )2 (AAT)] 7.05–7.99 (m, aromatic), 8.3 (s, CH N), 3.16 (s, CH2 ), 4.56 (s, NH2 ), 1.6 (s, CH3 ) a
[Ru(CO)(AsPh3 )2 (ATT)] 7.0–7.90 (m, aromatic), 8.26 (s, CH N), 3.13 (s, CH2 ), 4.51 (s, NH2 ), 1.6 (s, CH3 ) a
[Ru(CO)(PPh3 )(py)(ATT)] 7.03–7.92 (m, aromatic), 8.32 (s, CH N), 3.19 (s, CH2 ), 4.45 (s, NH2 ), 1.63 (s, CH3 ) 28.45

a: not recorded.

determine the geometry of the complexes (Table 3). The appear-

ance of a singlet around 28.65–28.72 ppm in the spectrum of
complexes confirmed the presence of magnetically equivalent
phosphorous atoms, suggesting that the two PPh3 groups are
trans to each other [21].
Based on the analytical and spectral (IR, electronic, 1 H and
31 P NMR) data, an octahedral structure (Fig. 3) has been pro-

posed for all the ruthenium(II) Schiff base complexes.

3.2. Catalytic activity

The oxidation of alcohols was carried out with the ruthenium

complexes as catalyst in the presence of N-methylmorpholine-
N-oxide (NMO) as co-oxidant in chloroform (Table 4).
Benzaldehyde was formed from benzyl alcohol and cyclohex- Fig. 3. Structure of new Ru(II) complexes.

Table 4
Catalytic oxidation of alcoholsa by Ru(II) complexes in presence of NMO

Complex Substrate Product Yieldb (%) Turnoverc

[Ru(CO)(PPh3 )2 (AAT)] Benzyl alcohol A 34.31 94.26

Cyclohexanol K 26.21 71.57
[Ru(CO)(PPh3 )2 (ATT)] Benzyl alcohol A 32.60 89.55
Cyclohexanol K 24.38 68.27
[Ru(CO)(PPh3 )2 (CAT)] Benzyl alcohol A 35.00 96.22
Cyclohexanol K 25.01 70.11
[Ru(CO)(AsPh3 )2 (AAT)] Benzyl alcohol A 35.34 97.16
Cyclohexanol K 23.67 67.52
[Ru(CO)(AsPh3 )2 (ATT)] Benzyl alcohol A 34.66 95.28
Cyclohexanol K 27.01 72.21
[Ru(CO)(AsPh3 )2 (CAT)] Benzyl alcohol A 35.69 98.11
Cyclohexanol K 26.15 70.17
[Ru(CO)(PPh3 )(py)(AAT)] Benzyl alcohol A 32.60 89.55
Cyclohexanol K 21.27 64.85
[Ru(CO)(PPh3 )(py)(ATT)] Benzyl alcohol A 33.29 91.50
Cyclohexanol K 22.08 65.57
[Ru(CO)(PPh3 )(py)(CAT)] Benzyl alcohol A 33.63 92.45
Cyclohexanol K 23.98 67.27
[Ru(CO)(PPh3 )(pip)(AAT)] Benzyl alcohol A 33.21 91.42
Cyclohexanol K 23.89 67.77
[Ru(CO)(PPh3 )(pip)(ATT)] Benzyl alcohol A 32.92 83.27
Cyclohexanol K 20.87 65.19
[Ru(CO)(PPh3 )(pip)(CAT)] Benzyl alcohol A 30.31 84.86
Cyclohexanol K 20.97 64.29
a A: benzaldehyde; K: cyclohexanone.
b Yields based on substrate.
c Moles of product per mole of catalyst.
54 K.P. Balasubramanian et al. / Spectrochimica Acta Part A 68 (2007) 50–54

Table 5
Antibacterial activity data of ligands and Ru(II) complexes
Compound Diameter of inhibition zone (mm)

E. coli Aeromonas hydrophilla Salmonella typhi

0.25 % 0.5% 1% 0.25% 0.5% 1% 0.25% 0.5% 1%

H2 AAT 9 13 14 9 12 13 10 14 15
[Ru(CO)(PPh3 )2 (AAT)] 11 16 17 10 14 16 12 19 20
[Ru(CO)(PPh3 )(py)(AAT)] 11 15 18 10 15 17 13 17 21
H2 ATT 10 12 15 10 12 15 10 12 14
[Ru(CO)(PPh3 )2 (ATT)] 12 14 18 11 14 18 14 16 19
[Ru(CO)(AsPh3 )2 (ATT)] 13 17 20 15 17 21 15 14 20
H2 CAT 13 16 16 13 14 15 15 14 15
[Ru(CO)(PPh3 )(py)(CAT)] 16 17 19 14 15 17 17 16 19
[Ru(CO)(PPh3 )(pip)(CAT)] 15 14 17 18 19 22 22 20 22
Streptomycin 22 23 28 21 23 27 29 21 25

anol was converted into cyclohexanone after stirring for 3 h at References

room temperature. The products formed were quantified as their
2,4-dinitrophenylhydrazone derivatives. In no case, there was
any detectable oxidation of alcohols in the presence of NMO
alone and without ruthenium complexes. All of the synthesized
ruthenium complexes were found to catalyze the oxidation of
alcohols to carbonyl compounds but the yield and turnover were
found to vary with different catalysts. The yield and turnover
number are comparable with those reported for the oxidation
of alcohols by similar ruthenium(II) complexes [21]. It has also
been found that PPh3 complexes possess higher catalytic activity
than the AsPh3 complexes. This may be due to the higher donor
ability of the arsine ligand compared to the phosphine ligand.
The relatively higher product yield obtained for the oxidation
of benzyl alcohol than for cyclohexanol is due to the fact that
the ␣-CH moiety of benzyl alcohol is more acidic compared to
that of cyclohexanol [21]. The catalytic oxidation is expected
to proceed via Ru(IV) O intermediate as reported by us earlier
[14].
3.3. Antimicrobial study
The ligands and their complexes have been tested for in
vitro growth inhibitory activity against E. coli, Aeromonas
hydrophilla and Salmonella typhi by using the disc diffusion
method [22]. From the results (Table 5), it is concluded that all
of the complexes exhibit moderate activity against all species of
bacteria used in this study. The variation in the toxicity of dif-
ferent complexes against different organisms depends either on
the impermeability of the cells of the microbes or differences in
ribosome in microbial cells [23]. The complexes are found to be
more toxic than their parent ligand. This is in conformity with
Tweedy’s chelation theory [24]. Besides, the toxicity increases
with increase in concentration of the test solution containing the
new complexes.
[1] G.F. de Sousa, C.A.L. Filgueiras, M.Y. Darensbourg, J.H. Reibenspies,
Inorg. Chem. 31 (1992) 3044.
[2] R. Prabhakaran, R. Karvembu, T. Hashimoto, K. Shimizu, K. Natarajan,
Inorg. Chim. Acta 358 (2005) 2093.
[3] A.R. Cowley, J.R. Dilworth, P.S. Donnelly, J.W. Shore, Dalton Trans.
(2003) 748.
[4] C. Paek, S.O. Kang, J. Ko, P.J. Corroll, Organometallics 16 (1997) 4755.
[5] E.K. John, M.A. Green, J. Med. Chem. 33 (1990) 1764.
[6] I.G. Santos, A. Hagenbach, U. Abram, Dalton Trans. (2004) 677.
[7] D.R. Prasad, G. Ferraudi, J. Phys. Chem. 86 (1982) 4037.
[8] G. Das, R. Shukla, S. Mandal, R. Singh, P.K. Bharadwaj, J.V. Hall, K.H.
Whitmire, Inorg. Chem. 36 (1997) 323.
[9] D.J. Jones, V.C. Gibson, S.M. Green, P.J. Maddox, Chem. Commun. (2002)
1038.
[10] N. Ahmed, J.J. Levision, S.D. Robinson, M.F. Uttley, Inorg. Synth. 15
(1974) 48.
[11] S. Gopinathan, I.R. Unny, S.S. Deshpande, C. Gopinathan, Ind. J. Chem.
25A (1986) 1015.
[12] R.A. Sanchez Delgade, W.Y. Lee, S.R. Choi, Y. Cho, M.J. Jun, Trans. Met.
Chem. 16 (1991) 241.
[13] K.P. Balasubramanian, R. Karvembu, V. Chinnusamy, K. Natarajan, Ind. J.
Chem. 44A (2005) 2450.
[14] V. Mahalingam, R. Karvembu, V. Chinnusamy, K. Natarajan, Spectrochim.
Acta Part A 64 (2006) 886.
[15] D.M. Boghaei, S. Mohebi, J. Mol. Cat. A: Chem. 179 (2002) 41.
[16] S.K. Dutta, D.B. Mc Conville, W.J. Youngs, M. Chaudhury, Inorg. Chem.
36. (1997) 2517.
[17] M.S. El-Shahawi, A.F. Shoair, Spectrochim. Acta Part A 60 (2004) 121.
[18] M.V. Kaveri, R. Prabhakaran, R. Karvembu, K. Natarajan, Spectrochim.
Acta Part A 61 (2005) 2915.
[19] R. Karvembu, S. Hemalatha, R. Prabhakaran, K. Natarajan, Inorg. Chem.
Commun. 6 (2003) 486.
[20] R. Karvembu, K. Natarajan, Polyhedron 21 (2002) 219.
[21] R. Karvembu, K. Natarajan, Polyhedron 21 (2002) 1721.
[22] C.H. Colins, P.M. Lyne, Microbial Methods, University Park Press, Balti-
more, 1970.
[23] P.G. Lawrence, P.L. Harold, O.G. Francis, Antibiot. Chemother. (1980)
1597.
[24] B.G. Tweedy, Phytopathology 55 (1964) 910.