Synthesis and characterization of ruthenium(III) chloride complexes with some 1,2-disubstituted benzimidazoles and their catalytic activity

Article abstract of DOI:10.1080/15533174.2011.568446

Reaction of ruthenium(III) chloride with 2-mono substituted and 1,2-disubstituted benzimidazoles yield the complexes of the formulae RuCl ₃L_y.nH₂O [L = 2-o-hydroxyphenylbenzimidazole (oHPB), y = 3, n = 0; L = 2-p-hydroxyphenylbenzimidazole (pHPB), y = 2, n = 3], and RuCl3L2.H2O [L = 1-o-hydroxybenzyl-2-o-hydroxyphenylbenzimidazole (oHBPB), 1-m-hydroxybenzyl-2-m-hydroxyphenylbenzimidazole (mHBPB), and 1-p-hydroxybenzyl-2-p-hydroxyphenylbenzimidazole (pHBPB)]. The complexes are characterized by elemental analysis, conductivity measurements, infrared, electronic, ¹H- and ¹³C-NMR spectral studies, as well as by thermal analysis. The complexes exhibit octahedral geometry. Some of the complexes act as potential catalyst towards transferhydrogenation. Copyright Taylor & Francis Group, LLC.

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Synthesis and Characterization of Ruthenium(III)
Chloride Complexes with Some 1,2-Disubstituted
Benzimidazoles and their Catalytic Activity
G. Krishnamurthy a
a Department of Chemistry, Sahyadri Science College (Autonomous) , Kuvempu
University , Karnataka , India
Published online: 11 Jul 2011.
To cite this article: G. Krishnamurthy (2011) Synthesis and Characterization of Ruthenium(III) Chloride Complexes with
Some 1,2-Disubstituted Benzimidazoles and their Catalytic Activity, Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry, 41:6, 590-597, DOI: 10.1080/15533174.2011.568446
To link to this article: http://dx.doi.org/10.1080/15533174.2011.568446
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:590–597, 2011
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.568446
Synthesis and Characterization of Ruthenium(III) Chloride
Complexes with Some 1,2-Disubstituted Benzimidazoles
and their Catalytic Activity
G. Krishnamurthy
Department of Chemistry, Sahyadri Science College (Autonomous), Kuvempu University, Karnataka,
India
other reactions involving organic substrates.[4–7] Herein, we
Reaction of ruthenium(III) chloride with 2-mono substituted
and 1,2-disubstituted benzimidazoles yield the complexes of the
formulae RuCl3Ly.nH2O [L = 2-o-hydroxyphenylbenzimidazole
(oHPB), y = 3, n = 0; L = 2-p-hydroxyphenylbenzimidazole
report the synthesis, characterization of some of complexes
of ruthenium(III)chloride with 2-mono substituted and 1,2-
disustituted benzimidazoles. The complexes were used as cat-
alysts for transferhydrogenation reactions to reduce aromatic
nitro compounds.[8–10]
(pHPB),
y
=
2,
n
=
3], and RuCl3L2.H2O [L
=
1-o-
hydroxybenzyl-2-o-hydroxyphenylbenzimidazole (oHBPB), 1-m-
hydroxybenzyl-2-m-hydroxyphenylbenzimidazole (mHBPB), and
1-p-hydroxybenzyl-2-p-hydroxyphenylbenzimidazole (pHBPB)].
The complexes are characterized by elemental analysis, conductiv-
ity measurements, infrared, electronic, 1H- and 13C-NMR spectral
studies, as well as by thermal analysis. The complexes exhibit oc-
tahedral geometry. Some of the complexes act as potential catalyst
towards transferhydrogenation.
EXPERIMENTAL
Reagents
The hydrated ruthenium(III) chloride was purchased
from Arora-Matthey, o-Phenylenediamine, salicylaldehyde,
m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde were
Merck / SD’s fine chemicals. The solvents used were Merck
chemicals and they were purified according literature meth-
ods.[11] Nitrobenzoic acids and nitoranilines (Riedel-de-Haem,
Germany) were recrystallized from methanol while nitrophe-
nols were used as procured. Formic acid (80%) was a BDH
chemical.
Keywords 1,2-disubstituted benzimidazoles, 13C-NMR spectral
studies, octahedral ruthenium(III) complexes, transferhy-
drogenation
INTRODUCTION
Ruthenium exhibits varied behavior compared to the other
platinum group metals in forming complexes. The metal also
shows a different coordination number for the same oxidation
number. This varied behavior of ruthenium is dependent to a
considerable extent on the nature of the ligands. The com-
plexes of ruthenium are of importance in view of their cat-
alytic activity towards several reactions such as polymerisa-
tion, photo-splitting of water, solar energy conversion,[1] hy-
droformylation,[2,3] isomerisation, transfer hydrogenation, and
Separation Procedures
When methanol was used as a solvent, the reaction mixture
was filtered and the filtrate was evaporated to dryness. Then the
obtained solid was dissolved in ether and dried over anhydrous
Na2SO4. The solvent ether was evaporated and the product was
recrystallized from methanol.
Transfer Hydrogenation Procedure
The reaction was carried out on a water bath, in a three-
necked round bottom flask, and reaction was monitored by thin
layer chromatographic technique.
Received 9 September 2010; accepted 1 February 2011.
This article is dedicated to Dr. N. Shashikala, the author’s research
guide, who passed away this previous year. The authorities of Central
Drug Research Institute Lucknow, India for CHN Analyses and the au-
Physical Methods
The microanalysis of carbon, hydrogen, and nitrogen of the
thorities of the Sophisticated Instrumentation Facility, Indian Institute compounds were carried out on a Carlo-Erba analyzer. The
of Science, Bangalore for recording NMR Spectra. The author is also
thankful to UGC New Delhi for financial assistance.
Address correspondence to G. Krishnamurthy, Department of
Chemistry, Sahyadri Science College (Autonomous), Kuvempu Uni-
versity, SHIMOGA 577 203, Karnataka, India. E-mail: gkm-
naik sahyadri@yahoo.co.in
IR spectra (in nujol) were recorded on a Nicolet 4000D spec-
trophotometer. Molar conductivity measurements were made in
dimethylformamide(DMF) using a digital conductivity meter-
304 (SYSTRONICS) with a conventional dip type conductivity
cell with a cell constant 1.00 cm−1. NMR spectra were recorded
590

CATALYTIC ACTIVITY OF NOVEL Ru(III)Cl3 COMPLEXES
591
OH
H
N
Cl
Cl
N
N
N
Ru
Cl
HN
NH
HO
OH
H2O
+
RNH2
RNO2
RNO
RNHOH
FIG. 1. Structure of complexes of benzimidazoles with RuCl3.
(in DMSO-d6) on Bruker WH-270 or AMX-400 MHz spec- brown/gray/black colored solid separated. The product was fil-
trometer using TMS as the internal standard. While a Shimadzu tered, washed with acetone, and dried in vacuo, yield 70–80%.
UV-Vis-NIR Model UV-3101pc and Hitachi-V3400 UV-visible-
spectrophotometer were used for recording the electronic spec-
RESULTS AND DISCUSSION
tra of the solid samples as nujol-mull. The thermograms were
The physical properties and analytical data of these com-
recorded on a Shimadzu Thermal Analyser DT30 at a heat-
plexes are compiled in Table 1. Reaction of ruthenium(III) chlo-
ing rate of 5◦C / minute. Magnetic susceptibility measurements
ride with 2-substitued benzimidazloes viz., oHPB, pHPB with
were carried out for solid samples on a Guoy magnetic bal-
1:3 and 1:2 molar ratio, respectively, in acetone/acetone-ethanol
ance at room temperature. The Guoy tube was calibrated us-
mixture to give the complexes of the formulae RuCl3Ly.nH2O
ing CuSO4.5H2O and Hg[Co(SCN)4]. Diamagnetic corrections
[L = oHPB, y = 3, n = 0; L = pHPB, y = 2, n = 3]. Simi-
larly, 1,2-disubstituted benzimidazoles viz., oHBPB, mHBPB,
and pHBPB in 1:2 molar ratio in acetone/acetone-ethanol mix-
ture yield black/gray/brown colored complexes of the formulae
[RuCl3L2(H2O)] [L = oHBPB, mHBPB and pHBPB]. The com-
plexes are soluble in common organic solvents and behave as
non-electrolytes in DMF.
The nujol mull infrared spectra (Table 2) of complexes are
comparable to those of uncoordinated ligands except for mi-
nor shifts in the positions of some of the bands. The spectra
of the complexes of oHPB and pHPB show bands at 3260
were applied using Pascal’s constant.[12] The effective magnetic
moments (µeff) were calculated from the corrected molar mag-
netic susceptibilities (χM) using the relation
ꢀ
µeff = 2.84 (χM)T,
where T is the absolute temperature (in Kelvin).
Preparation of Complexes
The ligands were prepared according to the literature meth- and 3203 cm−1, respectively, due to νNH of the ligand. The
ods.[4a-c] Hydrated ruthenium trichloride (1 mmol) in acetone νOH band is located around 3250 cm−1. The band due to wa-
(15 ml) was treated with acetone (10 ml) solution of the ligand ter of hydration[13–15] in the complex of pHPB is observed at
viz., oHPB, pHPB, oHBPB, mHBPB, and pHBPB (2 mmol), 3560 cm−1. The infrared spectrum of [RuCl3(oHBPB)2(H2O)]
one each taken at a time for obtaining different complexes. shows a band around 3220 cm−1 due to νOH of ligand whereas
The resulting solution was refluxed for 6 to 8 h, when a dark the complexes of mHBPB and pHBPB show νOH band at 3178
3
4
6'
5'
N
5
N
N
9
4'
2
1'
6
8
N
1
3'
2'
7
OH
CH2
1"
HO
H
6"
2"
3"
5"
OH
4"
oHPB
mHBPB
FIG. 2. Structure of the ligands.

592
G. KRISHNAMURTHY
TABLE 1
Physical properties and analytical data (%) of Ruthenium(III) complexes
Analytical data (%)∗
M.P. (◦C) µeff (B.M) ꢀa ꢁ−1cm2 mol−1 Carbon
Hydrogen Nitrogen
Complex
Color
Black
[RuCl3(oHPB)3]
[RuCl3(pHPB)2(OH2)].2H2O Brown
[RuCl3(oHBPB)2(H2O)]
[RuCl3(mHBPB)2(H2O)]
[RuCl3(pHBPB)2(H2O)]
>260
>260
>260
>260
>260
2.38
2.49
1.87
1.90
1.89
24
16
19
12
13
55.16 (55.88) 3.61 (3.61) 9.25 (10.00)
46.02 (45.80) 3.59 (3.84) 7.53 (8.20)
56.16 (55.99) 4.51 (3.99) 6.58 (6.53)
56.52 (55.99) 4.31 (3.99) 6.60 (6.53)
56.52 (55.99) 4.31 (3.99) 6.66 (6.53)
Brown
Gray
Gray
∗Calculated values are in the parentheses.
aMolar conductance of Ca 10−3M solution in DMF.
and 3206 cm−1, respectively. The sharp band around 1620 cm−1
is assigned to C = C and C = N stretching vibrations.[16–18]
The magnetic susceptibility of the complexes has been mea-
sured at ambient temperature, and the effective magnetic mo-
ments are in the range 1.87–2.49 B.M. The values are in the
expected range for the low spin octahedral Ruthenium(III) com-
plexes.[19–22] The values are slightly higher than the spin only
magnetic moment expected for one unpaired electron (1.73
B.M). The higher value of the magnetic moment indicates con-
siderable orbital contribution (as expected) to the total magnetic
TABLE 3
Electronic spectral data (cm−1) of some Ruthenium(III)
complexes
Electronic transitions and assignments
2T1g → T1g
2T2g
2A2g
→
2T2g
2T1g
→
4
Complex
(L → M)
[RuCl3(oHPB)3]
[RuCl3(pHPB)3].2H2O
25,000
27,170
17,760
17,240
17,000
15,080
18,520
16,000
11,870
16,120
11,900
14,280
moment of the unpaired electron[23,24]
.
[RuCl3(oHBPB)2(H2O)] 27,170
[RuCl3(mHPB)2(H2O)] 17,240
The solid state (in nujol mull) electronic spectra of the com-
plexes have been recorded and the data are compiled in Table
[RuCl3(pHPB)2(H2O)]
34,240
3. The bands at 17000 and 16000 cm−1 are assigned to 2T2g
→
2A2g, T1g transitions, respectively. The band observed around
2
27000 cm−1 is the lowest energy spin forbidden absorption cor-
spectra of [RuCl3(oHPB)3] and [RuCl3(pHPB)2(OH2)].2H2O
display a resonance signal at δ 13.70 and 13.25 ppm, respec-
tively, due to the proton of NH group. The resonance signal due
to the proton of OH moiety in the complex of oHPB is observed
at 10.53 ppm, while in the complex of pHPB it is obtained
at 10.80 ppm. The resonance signals due to the protons of
the phenylene group in the complexes of oHPB and pHPB
are located in the range 7.09 and 8.86 ppm. The spectrum
of [RuCl3(oHBPB)2(OH2)] complex shows the resonance
2
4
responding to T2g → T1g transition, which is frequently ob-
served as a shoulder to L → M charge transfer transition. The
results reveal that only the tertiary nitrogen atoms are bonded to
the metal ion in an octahedral geometry.[23,25]
1
The H NMR spectra of the uncoordinated benzimidazoles
and their complexes were recorded in DMSO-d6 (Table 4). The
spectra of the complexes are almost similar to that of ligand
except for slight shifts in the positions of their peaks.[24,25] The
TABLE 2
Infrared spectral data (cm−1) of some Ruthenium(III) complexes
νOH of
νOH of lattice coordinated
νOH of νNH of νC C and
o-, m-, p-disubstituted
benzene ring
Complex
H2O
H2O
ligand
ligand
νC N
oHPB
[RuCl3(oHPB)3]
pHPB
[RuCl3(pHPB)2(OH2)].2H2O
[RuCl3(oHBPB)2(H2O)]
[RuCl3(mHBPB)2(H2O)]
[RuCl3(pHBPB)2(H2O)]
–
–
–
–
–
–
3220b
3230b
3210b
3203b
–
3324b
3328b
3375b
3384b
–
1620s
1626s
1648s
1641s
1618s
1620s
1624s
1490s, 1050m, 730s, 542w
1494s, 1054m, 736s, 548w
1480s, 1058w, 738s, 542w
1486s, 1054w, 736s, 546w
1492, 1056m, 735s, 548w
1290s, 1110s 724m, 540w
1460b, 1178m, 722m
3560b
–
3328b
3318b
3328b
3178b
3206b
–
–
s = strong, w = weak, b = broad

593

594
G. KRISHNAMURTHY
FIG. 4. Geometry of the complexes.
It is evident from the analytical data, molar conductance,
magnetic susceptibility measurements, infrared, electronic, 1H−
and 13C NMR spectra, and thermal analysis results that the
ligands are coordinated to the metal ion. The complexes are
expected to be six coordinated with pseudo octahedral geometry
with the ligands monodentately coordinated to the metal ion.
The structures 4 to 6 may be suggested for the complexes.
signals at 12.62 ppm due to protons of both benzyl and phenyl -
OH groups, whereas the complexes of [RuCl3(mHBPB)2(OH2)]
and [RuCl3(pHBPB)2(OH2)] show signals in the range 9.50 –
9.53 ppm and 10.01 – 10.46 ppm, respectively, due to benzyl
and phenyl group hydroxyl protons.
In the IR spectra of uncoordinated oHPBI and oHBPB, the
–OH stretching is not observed around 3200 cm−1, indicates the
hydrogen bonding, while in complexes appearance of the peak
indicate non-involvement of –OH group. It is further conformed
by 1H NMR, hence coordination via O-atom of hydroxyl group
has not occurred.
TRANSFER HYDROGENATION
Watanabe and coworkers[32] have studied the reduction of
RC6H4NO2 (R = H, 2-Me, 2-MeO, 2-Cl, 4-Me, 4-MeO, 4-
Cl) to RC6H4NH2 using formic acid as a hydrogen donor in
the presence of RuCl2(PPh3)3 as catalyst at moderate temper-
ature and pressure. Ruthenium(II) carbonyl complexes of the
type [RuL(CO)2Cl]2 [L = 2-phenylpyridine, 1-phenylpyrazole,
azobenzene] were used as catalysts for the reduction of aliphatic
and aromatic nitro compounds to amines.[32,33] We report here
transfer hydrogenation of aromatic nitro compounds using
[RuCl3(pHPB)3(OH2)].2H2O under homogeneous conditions
with formic acid as hydrogen donor in methanol and DMF
solvents. Various organo nitro compounds that have been used
are o-, m- and p- nitrophenols, nitroanilines, nitro benzoic acids,
3,5 dinitronaphthalene, p-dinitrobenzene, 3-nitrosalicylic acid,
and 5-nitrosalicylic acid. The hydrogen donor, formic acid de-
composes into CO2 and H2 in the presence of a catalyst, and
this could be used as a source of hydrogen.
The 13C NMR spectra (Table 5) of the complexes are almost
similar to those of uncoordinated ligands except for slight shifts
in the positions of some of the signals. The resonance signal due
to the primary carbon of the -CH2 group appears in the range
47.80 – 63.82 ppm. The resonance signals due to the benzyl
ring carbons of [RuCl3L2(H2O)] [L = oHBPB, mHBPB and
pHBPB] complexes appear in the range 111.08 – 157.07 ppm.
The resonance signals in the range 109.26 – 157.64 ppm are
due to the carbons of the phenyl group. The resonance signals
in the range 122.58 – 157.37 ppm are due to the tertiary and
secondary carbons of the benzimidazole ring. The coordination
induced shifts (c.i.s) in the range 0.21 – 6.56 ppm have been
noted. The large c.i.s occur at some carbon atoms is due to
change in the electron densities on carbon adjacent to donar
atom in complexes.[4b−c,27,28]
[RuCl3(oHPB)3] and [RuCl3(pHPB)2(OH2)].2H2O com-
plexes were subjected to thermogravimetric analysis in air with
a heating rate of 5◦C/minute (Table 6). The [RuCl3(oHPB)3]
complex shows that the loss of three molecules of chloride
ions around 210◦C. The continuous decrease of exotherm
upto 600◦C with a small deviation at 359◦C indicate
the loss of three molecules of ligand. In the case of
[RuCl3(pHPB)2(OH2)].2H2O, the loss of two molecules of wa-
ter of hydration takes place around 78◦C.[29–31] The loss of three
chloride ions and a molecule of water occurs around 320◦C.
A sharp exotherm between the temperatures 500 and 600◦C
corresponds to the loss of two ligands.
It was observed that m-nitro phenol was difficult to reduce
whereas o- and p-nitrophenols undergo reduction. The time
taken by o-nitrophenol was longer than that of p-nitrophenol.
The reduced products were confirmed by TLC, melting point,
and IR spectral data. The difficulty in reducing m-nitrophenol
may be due to the formation of hydrohalic acid during the re-
action, which may inhibit the reduction process due to the pres-
ence of electron donating –OH group, which tends to increase
the electron density on the nitro group and thereby lower the
polarization of the NO bonds,[34,35] leading to a slower rate of
hydrogenation. The catalyst-substrate ratio used was 1:100 in

595

596
G. KRISHNAMURTHY
TABLE 6
Thermogravimetric analysis data (%) of some Ruthenium(III) chloride complexes
Complex
Stage
Temperature
Weight loss (%)∗
Species lost
[RuCl3(oHPB)3]
1
2
1
2
3
230
600
80
320
600
10.4 (12.6)
81.0 (75.1)
5.7 (5.2)
24.4 (18.5)
62.9 (61.6)
3Cl
3L
2H2O
3Cl + H2O
2L
[RuCl3(pHPB)2(OH2)].2H2O
∗
Calculated values are in the parentheses.
the solvent CH3OH. The solvent system used for TLC was a
Hydrogenation of dinitro aromatic compounds in DMF at
mixture of di-isopropylether, ethyl acetate and acetic acid in refluxing temperature in the presence of HCOOH and the cata-
the ratio 10:10:1. The results are tabulated in Table 7. The lyst proceed via initial selective reduction of nitroaromatics and
solvent system used for TLC in the separation of product of hydrogenation of nitroaromatics to their corresponding amines
p-nitrobenzoic acids was a mixture of benzene, 1, 4-dioxan and at much more slower rate.
acetic acid in the ratio of 79:9:1. The products after the reduction
Since the reduction of aminonitroarenes is considerably
were tested by TLC, melting points and IR spectral data. Simi- slower than their rate of formation, selective reduction to a half
larly, for o-, m- and p-nitroanilines were used for the reduction, reduced stage could be achieved readily. The ability of the homo-
but none of the isomers could be reduced even after keeping for geneous catalyst to selectively hydrogenate 3, 5-dinitrobenzoic
a long time.[36,37]
acid and 1, 3-dinitrobenzene to their partially reduced species
In addition, the other nitro compounds, namely is advantageous to reduce dinitroaromatics sequentially in the
3-nitrosalicyclic acid, 5-nitrosalicylic acid, and 1- presence of mononitro compounds. The reason for the partial
nitronaphthalene, were tried under the same concentration. The reduction may be due to the inhibition of hydrogen transfer
solvents for TLC was a mixture of chloroform, ethylacetate, and from the donor to nitroamines due to the presence of the elec-
acetic acid in the ratio of 6:3:1 by volume. The appearance of tron donating group -NH2. Generally an increase in the electron
νNH peak in the range 3100–3300 cm−1 and the disappearance withdrawing nature of the para- substituent is associated by an
of νNO2 around 1600 cm−1, as well as the melting points, increase in the rate of hydrogenation. Conversely, the electron
support the completion of the reduction. The reduction of donating substituents, which tend to increase the electron den-
the nitro group may proceed via the formation of nitroso sity on the nitro group thereby lowering the polarization of the
compounds as intermediates, then to hydroxylamines, and N-O bonds, lead to slower rates of hydrogenation.
finally to amines, as shown below.
R−NO2 → R−NO → RNHOH → RNH2 + H2O
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