Polyhedron 29 (2010) 1175–1181

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Polyhedron
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Synthesis, crystal structure and catalytic activity of ruthenium(II) carbonyl

complexes containing ONO and ONS donor ligands
M. Ulaganatha Raja, N. Gowri, R. Ramesh *
School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, India

a r t i c l e i n f o a b s t r a c t

Article history: Diamagnetic ruthenium(II) complexes of the type [Ru(L)(CO)(B)(EPh3)] [where E = As, B = AsPh3; E = P,
Received 30 July 2009 B = PPh3, py (or) pip and L = dibasic tridentate ligands dehydroacetic acid semicarbazone (abbreviated
Accepted 7 December 2009 as dhasc) or dehydroacetic acid phenyl thiosemicarbazone (abbreviated as dhaptsc)] were synthesized
Available online 11 December 2009
from the reaction of [RuHCl(CO)(B)(EPh3)2] (where E = As, B = AsPh3; E = P, B = PPh3, py (or) pip) with dif-
ferent tridentate chelating ligands derived from dehydroacetic acid with semicarbazide or phenylthiose-
Keywords: micarbazide. All the complexes have been characterized by elemental analysis, FT-IR, UV–Vis and 1H
Ru(II) complexes
NMR spectral methods. The coordination mode of the ligands and the geometry of the complexes were
ONO/ONS donors
Crystal structure
confirmed by single crystal X-ray crystallography of one of the complexes [Ru(dhaptsc)(CO)(PPh3)2]
Redox property (5). All the complexes are redox active and are monitored by cyclic voltammetric technique. Further,
Catalytic oxidation the catalytic efficiency of one of the ruthenium complexes (5) was determined in the case of oxidation
of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of
N-methylmorpholine-N-oxide.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction of the stability of the complexes [14]. Thiosemicarbazones usually

Semicarbazones/thiosemicarbazones have emerged as an
important class of oxygen/sulfur donor ligands particularly for
transition metal ions in the last few decades [1–5]. In particular,
transition metal complexes of thiosemicarbazones have been
bind to a metal ion as bidentate N,S-donor ligands via dissociation
of the hydrazinic proton, forming five-membered chelate rings (3)
[15]. When a third donor site (D) is incorporated into the ligands,
linked to the carbonylic carbon via one or two intervening atoms,
normally D,N,S – tricoordination (4) takes place [16,17].

M D
R H X R XH M
C N N C NH2 C N N C NH2 N X X
N
R1 R1 N N
NH2 NH2
1 2 4
3
(X= O or S)

receiving considerable interest largely because of their pharmaco-

logical property [6–11]. The possibility of modulating the cytotoxic
activity by changing the structure of the complex was also proved
[12,13]. Thiosemicarbazones are versatile ligands which can coor-
dinate as neutral ligands (1) or in their deprotonated form (2). Li-
gands with additional donor groups such as –PR2, –NH2, –OH, or –
SH at the substituents R1 are of special interest since they can coor-
dinate in a tridentate fashion which results in a significant increase
* Corresponding author. Tel.: +91 431 2407053; fax: +91 431 2407045x2407020.
E-mail address: ramesh_bdu@yahoo.com (R. Ramesh).
Oxidation of alcohols to carbonyl compounds is an important
transformation in synthetic organic chemistry [18]. From both an
economic and environmental point of view, the quest for effective
catalytic systems that use clean, inexpensive primary oxidants,
such as molecular oxygen or hydrogen peroxide, i.e. a ‘green meth-
od’ for converting alcohols to carbonyl compounds on an industrial
scale, remains an important challenge [19]. Although several stoi-
chiometric reagents based on activated dimethyl sulfoxide (Swern
oxidation) [20], hypervalent iodine compounds (Dess-Martin) [21]
and reactive oxometal compounds [22] (MnO2 and pyridinium
chlorochromate) have been developed to display high degree of

0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.12.009
1176 M. Ulaganatha Raja et al. / Polyhedron 29 (2010) 1175–1181

selectivities, the search for new catalytic procedures for selective
alcohol oxidations using inexpensive oxidants such as H2O2
[23,24] and tert-butyl hydroperoxide (TBHP) [25] remains an area
of intensive interest. RuCl2(PPh3)3 and some high valent oxoruthe-
nium complexes are known to mediate alcohol oxidations using a
variety of oxidants such as PhIO [26], NaIO4 [27], molecular oxygen
[28], N-methylmorpholine N-oxide, BrO3 and S2O82 under mild
conditions [29]. The synthesis of aldehydes entails a selectivity
problem namely, their further oxidation to carboxylic acids –
which can only be overcome through the selection of an appropri-
ate oxidant. Ru-based oxidation catalysis is a powerful and extre-
mely versatile synthetic tool to afford selectively oxygenate
products both in homogeneous and in heterogeneous conversions
[30].
Over the past few years our group has been working on the
coordination chemistry of ruthenium complexes, characterization
and their catalytic applications [31–33]. In the present work, we
report the results of our study on synthesis of ruthenium(II) car-
bonyl complexes of dehydroacetic acid semicarbazone/phenylthi-
osemicarbazone incorporating PPh3/AsPh3 and nitrogen
heterocycles. The complexes have been characterized by physio-
chemical methods. The structure of one of the complexes has been
probed with the help of single crystal X-ray diffraction analysis.
Further, the electrochemical and catalytic properties of the com-
plexes were studied.
2. Experimental
2.2. Physical measurements
The analysis of carbon, hydrogen, nitrogen and sulfur were per-
formed at Sophisticated Test and Instrumentation Centre (STIC), Co-
chin University, Kochi. Infrared spectra of complexes were recorded
in KBr pellets with a Perkin–Elmer 597 spectrophotometer in the
range 4000–400 cm 1. Electronic spectra of the complexes were re-
corded in CHCl3 solution with a Cary 300 Bio UV–Vis Varian spectro-
photometer in the range 800–200 nm. The 1H NMR spectra were
recorded in CDCl3 and DMSO with Bruker 400 MHz instrument
using TMS as internal reference. Melting points were recorded in
the Boetius micro heating table and are uncorrected. Electrochem-
ical measurements were made using a Princeton EG and G-Parc
model potentiostat using a glassy carbon-working electrode and
[(n-C4H9)4N](ClO4) (TBAP) as supporting electrolyte. All the poten-
tials were referenced to Ag/AgCl electrode and the solutions were
purged with N2 before each set of experiments. The catalytic yields
were determined using HP 6890 series GC-FID with a DP-5 column
of 30 m length, 0.32 mm diameter and 0.25 mm film thickness.
2.3. Preparation of H2dhasc/ H2dhaptsc
To the hot solution of semicarbazide hydrochloride (0.223 g,
0.002 mol) or phenylthiosemicarbazide (0.334 g; 0.002 mol), hot
methanolic solution of dehydroacetic acid (0.336 g, 0.002 mol)
was added and refluxed for 3 h. On reducing the solvent, followed
by subsequent cooling, the solid product separated out and was
recrystallized from ethanol (Scheme 1). Yield = 72–78%.

2.1. Reagents and materials

2.4. Synthesis of ruthenium(II) carbonyl complexes of dhasc/ dhaptsc

Commercially available RuCl3
3H2O was used as supplied from

To a solution of 0.1 mmol of [RuHCl(CO)(B)(EPh3)2] (where
Loba Chemie. All the reagents used were chemically pure and ana-
E = As, B = AsPh3; E = P, B = PPh3, py or pip) in dry benzene
lytical grade. The solvents were freshly distilled using the standard
(20 ml) was added 0.1 mmol ligand H2dhasc/H2dhaptsc (mole ratio
procedures [34]. Dehydroacetic acid, semicarbazide and phenylthi-
of ruthenium complex and ligand is 1:1) and the mixture was re-
osemicarbazide were purchased from SRL. The supporting electro-
fluxed for 10 h (Scheme 2). The solution was concentrated to about
lyte tetrabutyl ammonium perchlorate (TBAP) was dried in
3 ml and petroleum ether was added where by the ruthenium(II)
vacuum prior to use. The alcohols and their corresponding ketones
semicarbazones/phenylthiosemicarbazones were separated. The
or aldehydes, which were used in the catalytic studies, were pur-
resulting complexes were recrystallized from CH2Cl2/petroleum
chased from Merck and Aldrich. The precursor complexes [RuHCl(-
ether and dried under vacuo. The purity of the complexes was
CO)(PPh3)3] [35], [RuHCl(CO)(B)(PPh3)2] [36] (where B = py or pip)
checked by TLC. Yield = 64–76%.
and [RuHCl(CO)(AsPh3)3] [37] and the ligands [38] were prepared
by reported literature methods.
2.5. X-ray crystallography

Single crystals of [Ru(dhaptsc)(CO)(PPh3)2] (5) were grown by

H3C H3C slow evaporation of chloroform solution at room temperature. A
X
CH3OH
OH
single crystal of suitable size was covered with Paratone oil,
O OH + H2N NH C O
reflux / 3h mounted on the top of a glass fiber, and transferred to a Stoe IPDS
NHR X
O C O O C N diffractometer using monochromated Mo Ka radiation
H3C H3C N C (kI = 0.71073). Data were collected at 183 K. Corrections were
H NHR made for Lorentz and polarization effects as well as for absorption
(R = H, X = O and R = C6H5, X = S) (numerical). The structure was solved with direct method using
SIR-97 [39,40] and was refined by full-matrix least-squares meth-
Scheme 1. Preparation of H2dhasc and H2dhaptsc ligands.
od [41] on F2 with SHELXL-97. Non-hydrogen atoms were refined

H3C H3C
EPh3
O OH C6H6 O O CO
[RuHCl(CO)(B)(EPh3)2] Ru
+ X
O C N X reflux/10h O N
H3C B
H3C N C NHR N C
H NHR
(E = P or As; B = py, pip, PPh 3, AsPh 3; R = H, X=O; R = C6H5, X= S )

Scheme 2. Synthesis of ruthenium(II) carbonyl complexes of dhasc/dhaptsc.

 M. Ulaganatha Raja et al. / Polyhedron 29 (2010) 1175–1181 1177

with anisotropy thermal parameters. All hydrogen atoms were
geometrically fixed and allowed to refine using a riding model.
2.6. Catalytic oxidation
Catalytic oxidation of primary alcohols to the corresponding
aldehydes and secondary alcohols to ketones by ruthenium(II)
carbonyl complexes was studied in the presence of NMO as co-oxi-
dant. A typical reaction using the complex [Ru(dhaptsc)
(CO)(PPh3)2] (5) as a catalyst and primary or secondary alcohol
as substrates at a 1:100 molar ratio is described as follows. A solu-
tion of ruthenium complex (5) (0.01 mmol) in 20 cm3 CH2Cl2 was
added to the solution of substrate (1 mmol) and NMO (3 mmol).
The solution mixture was refluxed for 3–8 h and the solvent was
then evaporated from the mother liquor under reduced pressure.
The residue was then extracted with diethyl ether (20 cm3) and
was analyzed by GC. The oxidized products were determined by
GC by comparison with authentic samples.
3. Results and discussion
The new ruthenium(II) carbonyl complexes of dehydroacetic
acid semicarbazone/phenylthiosemicarbazone of the type [Ru(L)-
(CO)(B)(EPh3)], (where L = dhasc or dhaptsc) (Scheme 2) have been
obtained from the reaction of [RuHCl(CO)(B)(EPh3)2] (where E = P,
B = PPh3, py or pip; E = As, B = AsPh3) with tridentate Schiff base
H2dhasc/H2dhaptsc in dry benzene in 1:1 molar ratio. All the
new ruthenium(II) carbonyl complexes are colored, stable to air
and light and soluble in dichloromethane, benzene, DMF, DMSO.
The analytical data are given in Table 1 and are in good agreement
with the general molecular formula proposed.
3.1. Characterization
In IR spectra, the free ligands display mC@O/mC@S absorption at
1685 cm 1/788 cm 1. The absence of mO–H/mS–H in the free ligand
suggests that they are exists in the ketone/thione form. The new
band appeared around 1188–1182 cm 1 which corresponds to
mC–O for semicarbazone complexes and the mC–S appeared at
1275–1240 cm 1 in phenyl thiosemicarbazone complexes. The IR
spectra of the complexes did not display mO–H/mS–H at 3419–
3409 cm 1/2585–2570 cm 1 suggesting the deprotonation of the
enol/thiol proton prior to coordination. The strong band at 1627–
1622 cm 1 in the ligand which is characteristic of the azomethine
(C@N) group is shifted to lower frequency (1557–1524 cm 1) in all
the complexes [42]. The strong band observed at 1247 cm 1 in the
ligand due to enolic mC–O stretching shifts to higher frequency in
the range 1262–1258 cm 1 in the complexes, indicating that the
coordination through the enolic oxygen atom [43]. For all the com-
plexes, a new strong band in the region 1953–1939 cm 1 due to
the terminally coordinated carbonyl group is observed which is
at higher frequency than in the precursor complexes (Table 2).
The spectra of the free ligands show strong bands at 1686–
1661 cm 1 for (mC@O) lactone carbonyl groups and are observed un-
changed in the ruthenium chelates, inferring that the lactone car-
bonyl group are not involved in the coordination. Further, the
complexes show a strong band near 530, 690, 740 and
1556 cm 1, which are due to PPh3/AsPh3 ligands. A medium inten-
sity band is observed at 1092 cm 1 characteristic of the coordi-
nated pyridine or piperidine [44]. Bands in the region 410–
400 cm 1 are due to M–O, M–N and M–S stretching.
The electronic spectra of the complexes in CHCl3 showed two
bands in the region 382–252 nm (Table 2). The ground state of
ruthenium(II) is 1A1g, arising from the t62g configuration in an octa-
hedral environment. Excited state corresponding to the t52g e1g
configuration are 3T1g, 3T2g, 1T1g, 1T2g. Hence, four bands corre-
sponding to the transitions 1A1g ? 3T1g, 1A1g ? 3T2g, 1A1g ? 1T1g
and 1A1g ? 1T2g are possible, in order of increasing energy. The
bands in the 382–318 nm region present in all the complexes
may be assigned to the Ru(4dp) ? p* (imine) (MLCT) transition
[45–47]. The other high intensity bands in the 282–252 nm region
were characterized by ligand-centered (LC) transitions and have
been designated as p–p* and n–p* transitions for the electrons
localized on the azomethine group of the Schiff bases. The pattern

Table 1
Analytical data of ruthenium(II) carbonyl complexes of dhasc/dhaptsc.

SI. No. Complexes Calculated (found) (%)

C H N S
1 [Ru(dhasc)(CO)(PPh3)2] 58.80(58.88) 4.53(4.520) 4.74(4.75)
2 [Ru(dhasc)(CO)(py)(PPh3)] 57.03(57.05) 4.32(4.30) 8.06(8.10)
3 [Ru(dhasc)(CO)(pip)(PPh3)] 56.62(56.65) 5.00(5.02) 8.00(8.02)
4 [Ru(dhasc)(CO)(AsPh3)2] 57.13(56.08) 4.17(4.14) 4.30(4.34)
5 [Ru(dhaptsc)(CO)(PPh3)2] 64.35(64.39) 4.53(4.51) 4.33(4.35) 3.30(3.32)
6 [Ru(dhaptsc)(CO)(py)(PPh3)] 59.55(59.51) 4.35(4.39) 7.14(7.11) 4.01(4.02)
7 [Ru(dhaptsc)(CO)(pip)(PPh3)] 59.14(59.11) 4.92(4.88) 7.01(6.99) 4.04(4.00)
8 [Ru(dhaptsc)(CO)(AsPh3)2] 59.00(59.05) 4.16(4.17) 3.90(3.89) 3.02(3.01)

Table 2
IR and electronic spectral data of ruthenium(II) carbonyl complexes of dhasc/dhaptsc.
1
Complexes Important frequencies (cm ) kmax (nm)(e)(dm3 mol 1
cm 1
)
m(C„O) m(C@O) lactone) m(C@N) m(C–O)+m(C–S) phenolic)
1 1942 1661 1535 1258 318(13,548)a, 252(30,209)b
2 1939 1670 1524 1262 330(30,000)a, 268(51,612)b
3 1950 1675 1528 1275 324(31,080)a, 261(57,387)b
4 1948 1675 1537 1264 347(24,548)a, 264(68,193)b
5 1953 1685 1555 1246 380(16,806)a, 275(67,483)b
6 1952 1684 1557 1258 380(19,500)a, 282(48,887)b
7 1952 1684 1557 1240 379(24,451)a, 280(63,419)b
8 1951 1686 1554 1246 382(21,354)a, 269(52,403)b
a
= MLCT.
b
= Intra-ligand charge transfer.
1178 M. Ulaganatha Raja et al. / Polyhedron 29 (2010) 1175–1181

Table 3
1
H NMR spectral data of Ru(II) carbonyl complexes of dhasc/dhaptsc.
1
Complexes H NMR data (ppm)
Ar–H (m) NH2 (s) @CH (s) CNCH3 (s) CH3 (ring) (s) NH (s)
1 7.2–7.9 3.4 5.4 2.2 1.8
2 7.0–7.8 3.3 5.3 2.1 1.7
3 7.0–7.9 3.2 5.3 2.2 1.8 9.2
4 7.1–7.8 3.4 5.4 2.0 1.9
5 7.2–8.0 5.4 2.1 1.7 4.2
6 7.0–7.8 5.3 2.1 1.8 4.3
7 7.1–7.9 5.1 2.1 1.8 4.1 and 9.5
8 7.0–7.8 5.2 2.3 1.9 4.3

Table 4
Crystal data and structure refinement for complex (5).

Empirical formula C52H43N3O4P2RuS

Formula weight 968.96
Temperature (K) 183(2)
Wavelength (Å) 0.71073
Crystal system triclinic
Space group P1

Unit cell dimensions

a = 12.004 (Å)
b = 12.891 (Å)
c = 15.863 (Å)
a = 80.32 (°)
b = 80.07 (°)
c = 68.06 (°)
Volume (Å3) 2228.3
Z 2
Dcalc (Mg/m3) 1.444
Absorption coefficient (mm 1) 0.521
F(0 0 0) 996
Crystal size (mm3) 0.21  0.15  0.12
Theta range for data collection (°) 2.93–22.50
Fig. 1. 1H-NMR spectrum of complex [Ru(dhaptsc)(CO)(PPh3)2] (5). Index ranges 12  h  12, 13  k  13,
17  l  16
Reflections collected 15347
of the electronic spectra of all the complexes indicate the presence Independent reflections 5523 [R(int) = 0.0433]
of an octahedral geometry around ruthenium(II) ion [48]. Completeness to theta = 22.50° 95.0%
Absorption correction numerical
The bonding arrangement is further confirmed by 1H NMR spec-
Maximum and minimum 0.9568 and 0.9234
tra (Table 3) and the representative spectrum is shown in Fig. 1. In transmission
the spectra of all the complexes, the multiplet observed at around Refinement method full-matrix least-squares on F2
7.0–7.9 ppm is assigned to aromatic protons of the phenyl group of Data/restraints/parameters 5523/0/571
triphenylphosphine/triphenylarsine, the Schiff base and the het- Goodness-of-fit (GOF) on F2 1.128
Final R indices [I > 2r(I)] R1 = 0.0594, wR2 = 0.1604
erocyclic nitrogen base pyridine. The methine proton appeared as
R indices (all data) R1 = 0.0687, wR2 = 0.1652
a singlet around 5.1–5.4 ppm region. The CH3 protons at azome- Extinction coefficient 0.0032(14)
thine group appeared as a singlet at 2.0–2.3 ppm and the ring Largest diff. peak and hole (e Å 3
) 0.640 and 0.693
CH3 proton as singlet at 1.7–1.9 ppm. The piperidine CH2 and the
NH proton appeared at 1.4–2.5 and 9.2–9.5 ppm, respectively. In
the NH phenyl group, the NH comes around 4.1–4.3 ppm.
Ru(1)–O(2), 2.096(5) Å Ru(1)–N(1) and 2.3710(14) Å Ru(1)–S(1).
The coordinated ligand and carbonyl constitute one equatorial
3.2. X-ray structure
plane with the metal at the center and the CO group is trans to
the azomethine (–C@N–) nitrogen. The two PPh3 ligands are mutu-
Further, a solid state molecular structure of the complex (5)
ally trans to each other. Usually the PPh3 ligands prefer to occupy
[Ru(dhaptsc)(CO)(PPh3)2] was resolved by single crystal X-ray
mutually cis positions for better p-interaction [2]. The presence
crystallography. The summary of the refinement parameters are gi-
of CO in these complexes is a strong p-acidic ligand, has probably
ven in Table 4 and the selected bond lengths and bond angles are
forced the bulky PPh3 to take up mutually trans position for steric
given in Table S1 (Supplementary content). An ORTEP view of the
reasons. The Ru–C bond length 1.833(7) Å in Ru(1)–C(1) fragment
complex (5) (Fig. 2) shows clearly that the thiosemicarbazone li-
is quite normal like that in the other structurally characterized
gand coordinates in a tridentate manner to ruthenium ion via the
ruthenium carbonyl complexes [49,50].
enolic oxygen, azomethine nitrogen and thiolate sulfur in addition
to two PPh3 and one carbonyl groups. Ruthenium is therefore sit-
ting in a NSOP2C coordination environment, which is distorted 3.3. Electrochemical study
octahedral in nature as reflected in all the bond parameters around
ruthenium. The thiosemicarbazone ligand binds the metal center As the ligand used in this work are not reversibly reduced or
at O, N and S forming one five-membered and one six-membered oxidized within the potential limits employed, we believe that
chelate ring with bite angles of 88.52(16)° O(2)–Ru(1)–N(1) and the redox processes observed for the complexes are metal centered
82.53(12)° N(1)–Ru(1)–S(1) and bond lengths of 2.071(4) Å only. Electrochemical study was carried out for all the Ru(II) car-
 M. Ulaganatha Raja et al. / Polyhedron 29 (2010) 1175–1181 1179

Fig. 2. The ORTEP diagram of the complex [Ru(dhaptsc)(CO)(PPh3)2] (5), hydrogen atoms have been omitted for clarity.

bonyl complexes in degassed acetonitrile solution at a glassy car-
bon-working electrode. The supporting electrolyte used was
0.05 M [Bu4N]ClO4 and the concentration of the complex is
10 3 M. A representative voltammogram is shown in Fig. 3.
All the complexes display a quasi-reversible oxidation and an
irreversible reduction at the scan rate of 100 mV s 1. The oxidation
observed is quasi-reversible in nature by a rather large peak-to-
peak separation (DEp) of 114–206 mV and the cathodic peak cur-
rent (ipc) is less than the anodic peak current (ipa). The one electron
nature of this oxidation has been verified by comparing its current
height (ipa) with that of the standard ferrocene-ferrocenium couple
under identical experimental conditions. Further an irreversible
reduction peak is observed in the range 0.76 V to 0.86 V. The
irreversibility observed for reduction response for all the com-
plexes may be due to short lived reduced state of metal ion [51]
or due to oxidative degradation of the ligands [52]. It has also been
observed that there is not much variation in the redox potential
due to the replacement of triphenylphosphine/triphenylarsine by
pyridine or piperidine.

3.4. Catalytic activity in the oxidation of alcohols

Ruthenium mediated oxidations are finding increasing applica-

tion due to the unique properties of this extremely versatile tran-
Fig. 3. Cyclic voltammogram of complex [Ru(dhaptsc)(CO)(PPh3)2] (5).
sition metal, whose oxidation states can vary from 2 to +8 and
this prompted us to carry out this type of reaction. The present
O
work describes the catalytic oxidation of primary and secondary
H2O + RuII NMO alcohols by the synthesized ruthenium(II) complex [Ru(dha-
R R' ptsc)(CO)(PPh3)2] (5) in CH2Cl2 in the presence of NMO and the
byproduct water was removed by using about 0.25 g of molecular
sieves (Scheme 3).
Complex (5) oxidizes primary alcohols to corresponding alde-
hydes and secondary alcohols to ketones with moderate to high
OH conversion and the results are listed in Table 5 (entries 1–10).
RuIV=O NM The aldehydes or ketones formed after 3 or 8 h of refluxing were
R R'
determined by GC and there was no detectable oxidation in the ab-
R, R' = alkyl (or) aryl
sence of ruthenium complex. Results of the present investigation
Scheme 3. Proposed catalytic cycle for the oxidation of alcohols by [Ru(dha- suggest that the complexes are able to react efficiently with
ptsc)(CO)(PPh3)2] (5). NMO to yield high valent ruthenium-oxo species responsible for
1180 M. Ulaganatha Raja et al. / Polyhedron 29 (2010) 1175–1181

Table 5
Catalytic oxidation of alcohols by [Ru(dhaptsc)(CO)(PPh3)2] (5).

Entry Substrates Products Time (h) Conversion (%) TON

1 OH CHO 3/8 61/76 61/76

2 OH O 3 92 92

3 OH O 3 >99 99

4 OH O 3 98 98

5 OH O 3 95 95

6 OH O 3 92 92

7 OH O 3 89 89

8 OH O 3/8 68/82 68/82

9 OH O 3/8 69/85 69/85

10 OH O 3 82 82

Substrate (1 mmol); NMO (3 mmol); complex (0.01 mmol); solvent dichloromethane. Yields determined by GC. TON = moles of product per mole of catalyst.

dehydrogenation of alcohols. This was further supported by spec-
tral changes that occur by addition of NMO to a dichloromethane
solution of the ruthenium(II) complex.
The appearance of peak at 392 nm is attributed to the formation
of RuIV@O species (Fig. 4), which is in conformity with other oxo
ruthenium(II) complexes [53,54]. Further support in favor of the
formation of such species is identified by the IR spectrum of the so-
lid mass (obtained by evaporation of the resultant solution to dry-
ness), which shows a band at 862 cm 1, characteristic of RuIV@O
species [55].
The oxidation of benzylalcohol to benzaldehyde results in 61%
conversion in 3 h and the maximum conversion 76% was obtained
after 8 h. The complex catalyzes the oxidation of 1-phenyl ethanol
into corresponding ketones in 92% yield. In the case of diphenyl-
methanol the oxidation product benzophenone is 99%. Interest-
ingly, the complex efficiently catalyzes the oxidation of five, six,
seven and eight-membered cyclic alcohols to the corresponding
ketones with conversions >89%, respectively. Further, the com-
plexes effectively catalyze the aliphatic alcohols like butan-2-ol
and pentan-2-ol to the corresponding ketones with moderate con-
versions in 3 h and the conversion were improved to 82% and 85%,
respectively after 8 h. It has been observed that the present cata-
lyst (5) has better catalytic efficiency in the oxidation of alcohols
than the previous report on similar ruthenium complexes [56].

4. Conclusion

Ruthenium(II) carbonyl complexes have the general formula

Fig. 4. Spectra of complex [Ru(dhaptsc)(CO)(PPh3)2] (5) + NMO (spectra taken after
20 min of mixing) in dichloromethane.
[Ru(L)(CO)(B)(EPh3)] (where, E = P, B = PPh3, py or pip; E = As,
B = AsPh3; L = dhasc/dhaptsc) have been synthesized. Analytical,
spectral (IR, UV–Vis, 1H NMR) and X-ray diffraction studies reveal
that the ligand coordinated to ruthenium in a tridentate fashion
and the ruthenium is present in a distorted octahedral environ-
ment. All the complexes show quasi-reversible oxidation and an
irreversible reduction waves. One of the complexes (5) was taken
 M. Ulaganatha Raja et al. / Polyhedron 29 (2010) 1175–1181
as model catalyst for the oxidation of alcohols to carbonyl com-
pounds in the presence of NMO and decent conversions were
obtained.
Acknowledgements
We gratefully acknowledge financial support from the Depart-
ment of Science and Technology (DST Ref. No. SR/S1/IC-03/2007)
New Delhi, India. M.U.R. thanks DST for the award of Senior Re-
search Fellowship (SRF).We express sincere thanks to Dr. B. Spin-
gler, Institute of Inorganic Chemistry, University of Zürich,
Switzerland for crystallographic discussion.
Appendix A. Supplementary data
CCDC 733343 contains the supplementary crystallographic data
for complex (5). These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.poly.2009.12.009.
References
[1] C. Paek, S.O. Kang, J. Ko, P.J. Coroll, Organometallics 16 (1997) 4755.
[2] F. Basuli, S.M. Peng, S. Bhattacharya, Inorg. Chem. 40 (2001) 1126.
[3] A.R. Cowley, J.R. Dilworth, P.S. Donnelly, A.D. Gee, J.M. Heslop, Dalton Trans. 16
(2004) 2404.
[4] M. Joseph, M. Kuriakose, M.R.P. Kurup, E. Suresh, A. Kishore, S.G. Bhatt,
Polyhedron 25 (2006) 61.
[5] A.E. Graminha, A.A. Batista, J. Ellena, E.E. Castellano, L.R. Teixeira, I.C. Mendes,
H. Beraldo, J. Mol. Struct. 875 (2008) 219.
[6] E.W. Ainscough, A.M. Brodie, W.A. Denny, G.J. Finlay, J.D. Ranford, J. Inorg.
Biochem. 70 (1998) 175.
[7] J.G. Tojal, J.L. Pizarro, A.G. Orad, A.R.P. Sanz, M. Ugalde, A.A. Diaz, J.L. Serra, M.I.
Arriortua, T. Rojo, J. Inorg. Biochem. 86 (2001) 627.
[8] M.R. Maurya, A. Kumar, A.R. Bhat, A. Azam, C. Bader, D. Rehder, Inorg. Chem. 45
(2006) 1260.
[9] S. Adsule, V. Barve, D. Chen, F. Ahmed, J. Med. Chem. 49 (2006) 7242.
[10] T. Bal, B. Atasever, Z. Solakoglu, S.E. Kuruca, B. Ulkuseven, Eur. J. Med. Chem. 42
(2007) 161.
[11] D.R. Richardson, D.S. Kalinowski, V. Richardson, P.C. Sharpe, D.B. Lovejoy, M.
Islam, P.V. Bernhardt, J. Med. Chem. 52 (2009) 1459.
[12] A.G. Quiroga, J.M. Perez, C. Alonso, C.N. Ranninger, Appl. Organomet. Chem. 12
(1998) 809.
[13] A.G. Quiroga, J.M. Perez, J.R. Masaguer, E. Montero, C. Alonso, C.N. Ranninger, J.
Inorg. Biochem. 70 (1998) 117.
[14] I.G. Santos, U. Abram, R. Alberto, E.V. Lopez, A. Sanchez, Inorg. Chem. 43 (2004)
1834.
1181
[15] Y.P. Tion, C.Y. Duan, Z.L. Lu, X.Z. You, H.K. Fun, S. Kandasamy, Polyhedron 15
(1996) 2263.
[16] P. Souza, I.A. Matesanz, V. Fernandez, J. Chem. Soc., Dalton Trans. 14 (1996)
3011.
[17] F. Basuli, S.M. Peng, S. Bhattacharya, Inorg. Chem. 36 (1997) 5645.
[18] I.E. Marko, P.R. Giles, M. Tsukazaki, I.C. Regnaut, C.J. Urch, S.M. Brown, J. Am.
Chem. Soc. 119 (1997) 12661.
[19] I.E. Marko, P.R. Giles, M. Tsukazaki, S.M. Brown, C.J. Urch, Science 274 (1996)
2044.
[20] L. Gentilucci, Y. Grijzen, L. Thijs, B. Zwanenburg, Tetrahedron Lett. 36 (1995)
4665.
[21] D.B. Dess, J.C. Martin, J. Org. Chem. 48 (1983) 4155.
[22] S.V. Ley, A. Madin, in: B.M. Trost, I. Fleming (Eds.), Comprehensive Organic
Synthesis, vol. 7, Pergamon, Oxford, 1991, pp. 251–289.
[23] K. Sato, M. Aoki, J. Takagi, R. Noyori, J. Am. Chem. Soc. 199 (1997) 12386.
[24] R.W. Murray, K. Iyanar, J.X. Chen, J. Wearing, Tetrahedron Lett. 36 (1995) 6415.
[25] J. Muzart, Chem. Rev. 92 (1992) 113.
[26] P. Muller, J. Godoy, Tetrahedron Lett. 22 (1981) 2361.
[27] V. Kesavan, D.B. Delpon, J.P. Begue, A. Srikanth, S. Chandrasekaran,
Tetrahedron Lett. 41 (2000) 3327.
[28] T. Nishimura, T. Onoue, K. Ohe, S. Uemura, J. Org. Chem. 64 (1999) 6750.
[29] W.P. Griffith, Chem. Soc. Rev. 21 (1992) 179.
[30] T. Naota, H. Takaya, S.I. Murahashi, Chem. Rev. 98 (1998) 2599.
[31] G. Venkatachalam, N. Raja, D. Pandiarajan, R. Ramesh, Spectrochim. Acta, Part
A 71 (2008) 884.
[32] K. Naresh Kumar, R. Ramesh, Y. Liu, Mol. Catal. A: Chem. 265 (2007) 218.
[33] G. Venkatachalam, R. Ramesh, S.M. Mobin, J. Organomet. Chem. 690 (2005)
3937.
[34] A.I. Vogel, Test Book of Practical Organic Chemistry, fifth ed., Longman,
London, 1989, p. 43.
[35] N. Ahmed, S.J. Levison, S.D. Robinson, M.F. Uttley, Inorg. Synth. 15 (1974) 48.
[36] S. Gopinathan, I.R. Unny, S.S. Deshpande, C. Gopinathan, Indian J. Chem. 25A
(1986) 1015.
[37] R.A. Sanchez-delgado, W.Y. Lee, S.R. Choi, Y. Cho, M.J. Jun, Transition Met.
Chem. 16 (1991) 241.
[38] D. Surya Rao, C. Sadasiva Reddy, V.T. John, Curr. Sci. 49 (1980) 511.
[39] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure Solution and
Refinement, University of Göttingen, Germany, 1997.
[40] A.D. Naik, S.M. Annigeri, U.B. Gangadharnath, V.K. Revankar, V.B. Mahale, J.
Mol. Struct. 616 (2002) 119.
[41] M.A. Ali, S.E. Livingstone, Coord. Chem. Rev. 13 (1974) 101.
[42] S.N. Pal, S. Pal, J. Chem. Soc., Dalton Trans. (2002) 2102–2108.
[43] S. Kannan, R. Ramesh, Polyhedron 25 (2006) 3095.
[44] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, Wiley Interscience, New York, 1971.
[45] O. Carugo, C.B. Castellani, Polyhedron 11 (1992) 21.
[46] K. Chichak, U. Jacquenard, N.R. Branda, Eur. J. Inorg. Chem. (2002) 357–368.
[47] F.A. El-Saied, A.A. El-asmy, W. Kaminsky, D.X. West, Transition Met. Chem. 28
(2003) 954.
[48] P. Sengupta, R. Dinda, S. Ghosh, Transition Met. Chem. 27 (2002) 665.
[49] R.S. Srivastava, F.R. Fronczek, Inorg. Chim. Acta. 322 (2001) 32.
[50] K. Naresh Kumar, R. Ramesh, Y. Liu, Inorg. Biochem. 100 (2006) 18.
[51] A.M. Bond, R. Colton, D.R. Mann, Inorg. Chem. 29 (1990) 4665.
[52] A. Basu, T.G. Kasan, N.Y. Sapre, Inorg. Chem. 27 (1988) 4539.
[53] A.M. El-Hendawy, A.H. Alkubaisi, A.E. Kourashy, M.M. Shanab, Polyhedron 12
(1993) 2343.
[54] W.H. Leung, C.M. Che, Inorg. Chem. 28 (1989) 4619.
[55] M.M.T. Khan, C. Sreelatha, S.A. Mirza, G. Ramachandriah, S.H.R. Abdi, Inorg.
Chim. Acta 154 (1988) 103.
[56] M. Sivagamasundari, R. Ramesh, Spectrochim. Acta, Part A 66 (2007) 427.