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Cobalt complexes of pyrrolecarboxamide ligands

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Cite this: Inorg. Chem. Front., 2017,

as catalysts in nitro reduction reactions: influence
4, 324 of electronic substituents on catalysis and
mechanistic insights†
Sunil Yadav, Sushil Kumar and Rajeev Gupta*

Received 20th September 2016,
Accepted 9th December 2016
DOI: 10.1039/c6qi00389c
rsc.li/frontiers-inorganic
This work presents two square-planar Co(III) complexes within a N4 coordination sphere created by two
related pyrrolecarboxamide ligands. Both complexes functioned as catalysts for the hydrazine-mediated
reduction of aromatic, heterocyclic, as well as aliphatic nitro substrates. Binding studies provided evidence
that the square-planar Co(III) complexes bind two equivalents of a substrate whereas mechanistic studies
established the involvement of a Co3+–Co2+ based redox cycle in the catalysis. The Co(III) complex having
electron-withdrawing –Cl substituents on the ligand was noted to be a much better catalyst than the one
with electron-donating –CH3 substituents.

Introduction reduction of a nitro group; and (ii) to gain mechanistic

Amines are important intermediates and key precursors in the
synthesis of various fine chemicals and pharmaceuticals and
therefore developing efficient and versatile catalysts for the
selective reduction of a nitro group has always been significant
yet challenging.1,2 Traditionally, the reduction of a nitro group
has been achieved using various precious3 as well as transition
metal based catalysts.2 In most cases, precious metal based
catalysts are found to be efficient for the nitro reduction.3
Efforts have also been made to develop heterogeneous catalysts
including nano-materials4 and a few unconventional materials
such as activated carbon,5 functionalized carbon nanotubes,6
graphene oxide,7 and assorted doped materials.8 Although
some of these alternative materials have been quite effective
but (i) their cumbersome synthesis to obtain the actual cata-
lyst; (ii) requirement of harsh reaction conditions; and (iii) ill-
explained reaction mechanism significantly hamper their
wider applicability. This reaction becomes even more challen-
ging when a nitro group is part of an aliphatic scaffold instead
of an arene ring;1 and for the substrates containing multiple
functional groups.1,2 Therefore, it is eminently desirable
although challenging (i) to develop efficient and non-precious
metal based less-expensive catalysts for the chemoselective
Department of Chemistry, University of Delhi, Delhi – 110 007, India.
E-mail: rgupta@chemistry.du.ac.in; http://people.du.ac.in/~rgupta/;
Tel: +91-11-27666646
† Electronic supplementary information (ESI) available. CCDC 1445062. For ESI
and crystallographic data in CIF or other electronic format see DOI: 10.1039/
c6qi00389c
insights about such a critical reaction. Herein, we present two
square-planar Co3+ complexes supported with pyrrolecarboxa-
mide ligands and their role in the chemoselective reduction of
assorted nitro compounds encompassing aromatic, hetero-
cyclic, and aliphatic substrates using hydrazine hydrate. The
binding studies infer that the square-planar Co3+ complexes
can interact with two equivalents of a potential substrate
whereas mechanistic studies substantiate the involvement of a
Co3+–Co2+ based redox cycle in the catalysis.
Results and discussion
Synthesis and characterization
This work utilizes two ligands, N,N′-(4,5-dichloro-1,2-
phenylene)bis(1H-pyrrole-2-carboxamide) (H4L1) and N,N′-(4,5-
dimethyl-1,2-phenylene)bis(1H-pyrrole-2-carboxamide) (H4L2),
which differ by the placement of either –Cl or –Me substi-
tuents on the phenylene ring.9 The reaction of the deproto-
nated form of the respective ligand with (Et4N)2[CoCl4] in DMF
followed by aerial oxidation affords Co(III) complexes 1 and 2
(Scheme 1). The disappearance of N–H stretches and a batho-
chromically shifted O-amide band affirms the bonding
through the deprotonated ligands in both complexes (Fig. S1
and S2, ESI†).9,10 Complexes 1 and 2 are deep purple in color
and display prominent absorption features at ca. 560 and
ca. 740 nm in CH3OH (Fig. S3, ESI†). The absorption spectra
recorded in CH3CN, CH3OH, and DMF displayed minor
changes in the spectral features suggesting potential co-
ordination of solvent molecule(s) in the solution state (Fig. S4

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perfect square-planar and tetrahedral geometries, respect-

ively.11 The sum of angles around the Co3+ ion is 359.8°, pretty
close to 360°, thus again suggesting a predominantly square-
planar geometry. Notably, 1 represents a rare example of a
mono-nuclear square-planar Co(III) complex as only a handful
compounds are known in the literature.12 Co(III) complexes
typically prefer an octahedral geometry, however, in case of
strong σ-donation, the axial Lewis acidity can be reduced to
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the point that a rare square-planar geometry becomes access-

ible as the case with complex 1.12b,d
Scheme 1 Synthetic routes for Co(III) complexes 1 and 2.
Solid-state variable-temperature (6–300 K) magnetic sus-
ceptibility studies exhibited that both complexes 1 and 2
follow the Curie–Weiss law over the temperature range of
60–300 K (Fig. S8, ESI†). At 300 K, μeff values of 3.2μB and 3.4μB
and S5, ESI†). It is therefore proposed that the solid-state four-
were observed for complexes 1 and 2, respectively. However,
coordinate Co(III) ion in complexes 1 and 2 is likely to interact
much reduced values of μeff both for 1 and 2 were noted at 6 K
with a suitable species and exceeds its coordination number,
suggesting the zero-field splitting.12b,13 These results are con-
at least in the solution state (vide infra). Both complexes are
sistent with the spin triplet (S = 1) ground state.12b,13 Both
sparingly soluble in H2O and therefore their absorption
complexes also displayed paramagnetically shifted 1H NMR
spectra could not be convincingly investigated; however,
spectra as expected for square-planar Co(III) complexes with
addition of excess H2O to a CH3OH solution of 1 and 2 did not
the S = 1 ground state.12b–d A representative spectrum of
result in an appreciable change (Fig. S6 and S7, ESI†).
complex 2, displayed in Fig. 2, clearly illustrates well-resolved
One of the representative compounds, complex 1, was struc-
protons resonating between 90 and −130 ppm. For example,
turally characterized. The crystal structure displays a nearly
pyrrole protons Hb, Hc, and Hd were noted as sharp reso-
square-planar geometry around the Co3+ ion wherein the
nances at −48, −13, and −127 ppm whereas arene-Ha was
ligand coordinates via two anionic Namide and two anionic
seen at 67 ppm. The –CH3 groups present on the arene ring
Npyrrole donors (Fig. 1). The average Co–Namide and Co–Npyrrole
were found to resonate at 89 ppm. A similar paramagnetically
bond distances were found to be 1.832 and 1.867 Å, respectively.9a,c
shifted 1H NMR spectrum was observed for complex 1
The five-membered metal-based chelate angles were smaller
(Fig. S9, ESI†).
than 90° therefore justifying a tight chelation around the
In cyclic voltammetric studies, both complexes display
cobalt center. The geometry around the Co3+ ion is a slightly
metal-based as well as ligand-based redox responses (Fig. 3).
distorted square-planar with a τ4 distortion parameter of
Complexes 1 and 2 exhibited reversible reductive responses at
0.15.11 For reference, τ4 has standard values of 0 and 1 for
−0.38 V (ΔE = 80 mV) and −0.48 V (ΔE = 85 mV), respectively
that has been assigned to the Co3+/2+ redox couple. In addition,
quasi-reversible oxidative responses at 0.30 V and 0.62 V for 1
and 0.14 V and 0.46 V for 2 have been tentatively suggested to
be ligand-centered. This assignment has been made by the
observation of oxidative responses in a similar range for our
earlier metal complexes supported with identical ligands.9a
Notably, the Co2+/+ redox couple was not observed within the

Fig. 1 Molecular structure of the anionic part of complex 1; thermal

ellipsoids are drawn at the 50% probability level whereas the Et4N+ ion
and hydrogen atoms have been omitted for clarity. Selected bond
distances (Å): Co–N1 = 1.881(7), Co–N2 = 1.837(7), Co–N3 = 1.828(7),
Co–N4 = 1.853(7). Selected bond angles (°): N1–Co–N2 = 85.1(3),
N1–Co–N3 = 169.1(3), N1–Co–N4 = 104.4(3), N2–Co–N3 = 84.7(3), Fig. 2 1H NMR spectrum of complex 2 recorded in CD3CN. * Represents
N2–Co–N4 = 170.0(3), N3–Co–N4 = 85.6(3). the residual solvent.

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supports both +3 as well as +2 oxidation states; (iii) contrast

electronic substituents (–Cl versus –CH3) could modulate the
electron density at the metal center as evidenced by the cyclic
voltammetric studies and such a fact may have a notable effect
on catalysis. Such structural and redox features advocated that
the present complexes are potential candidates for redox-
based catalysis.4c,16 We selected hydrazine-mediated nitro
reduction reactions to test the present complexes as cobalt has
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recently emerged as an efficient catalytic metal in assorted

Fig. 3 Cyclic voltammograms of complex 1 (green trace) and 2 (red
trace) recorded in MeOH at Pt working electrode; reference electrode:
Ag+/Ag; auxiliary electrode: Pt wire; scan rate: 100 mV s−1; supporting
electrolyte: 0.1 M TBAP.
solvent window for both complexes. We believe the tetra-
anionic ligands with high σ-donating abilities do not support
the Co(I) state in the present complexes.9,12 It is important to
note that the electron-withdrawing –Cl groups in 1 have
respectively shifted Co3+/2+ and other oxidative responses by
ca. 100 and ca. 150 mV towards positive potentials. 9a,14,15
Thus, it could be inferred that the Co3+ ion in complex 1 could
be easily reduced to Co2+ as a result of electron-withdrawing –Cl
substituents.
Nitro reduction reactions
Both complexes 1 and 2 offered several noteworthy features
which suggested their potential importance in catalysis: (i) the
square-planar Co3+ ion suggests uncluttered access of a sub-
strate; (ii) electrochemical studies illustrate that the cobalt ion
redox-based catalysis in general and nitro reduction in
particular.4c,16,17
An initial screening to identify the optimized reaction con-
ditions suggested that only 1 mol% of complex 1 was sufficient
for the hydrazine-based reduction of nitrobenzene. However,
for further optimization experiments, a challenging substrate
having a –CN group, para-CNPhNO2 was chosen as a model
substrate and complex 1 as a representative catalyst (Table 1).
The presence of complex 1 as a catalyst was essential as
the absence or presence of other cobalt salts (CoCl2,
(Et4N)2[CoCl4], or K3[Co(NO2)6]) as the catalysts did not result
in any reduction (entries 1 and 2, Table 1). Satisfyingly,
complex 1 quantitatively reduced para-CNPhNO2 in the pres-
ence of hydrazine in MeOH at 60 °C (entry 3, Table 1).
Hydrazine was found to be the most effective reducing agent
whereas H2, ammonium formate, NaBH4, formic acid, tri-
methylsilylsilane and triphenylsilane were mostly ineffective
although ca. 10% reduction was noted in the case of NaBH4
(entry 4). Entries 5 and 6 suggest the requirement of 60 °C as
the optimum temperature and 6 h duration for the quantita-
tive reduction. Entry 7 supports that only 2 equivalents of
NH2NH2 can quantitatively reduce para-CNPhNO2. Amongst
different solvents screened (entries 8–10), MeOH, EtOH, H2O,
acetone, toluene, and THF resulted in nearly quantitative

Table 1 Optimization and control experiments using para-CNPhNO2 as a model substrate with hydrazine and using complex 1 as a representative
catalysta

S. no. Catalyst Reducing agent Conditions Yieldb (%)

1 — NH2NH2 60 °C 0
2 CoCl2 or (Et4N)2[CoCl4] or NH2NH2 60 °C 0
K3[Co(NO2)6]
3 1 NH2NH2 60 °C 100
4 1 H2,c HCOONH4, NaBH4, HCOOH, 60 °C 0, 0, 10, 0, 0, 0
(SiMe3)3SiH, Ph3SiH
5 1 NH2NH2 20, 30, 40, 50, 60 °C 25, 28, 30, 95, 100
6 1 NH2NH2 1, 2, 3, 4, 5, 6 h 20, 30, 50, 70, 90, 100
7 1 NH2NH2 0.5, 1, 2, 3 equiv. 40, 55, 99, 100
8 1 NH2NH2 MeOH, EtOH, i-PrOH, n-BuOH, t-BuOH 100, 100, 27, 60, 53
9 1 NH2NH2 H2O, acetone, MeCN 98, 100, 87
10 1 NH2NH2 Toluene, THF, CHCl3, dioxane 100, 96, 46, 42
a
Reaction conditions: catalyst: 1 mol%; time: 6 h; solvent: MeOH except for entries 8–10. b Yield was calculated using the gas chromatograph. c 1 atm.

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Inorganic Chemistry Frontiers
reduction. Although water would have been the best solvent
but limited solubility of different nitro-substrates compelled
us to use MeOH in the subsequent work. To rule out whether
in situ formed Co nanoparticles were actually acting as a cata-
lyst, a Hg drop test was performed.18 Complex 1 quantitatively
reduced para-CNPhNO2 to para-CNPhNH2 using hydrazine in
the presence of a drop of mercury(0) thus eliminating the
involvement of nanoparticles during the catalysis.
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The optimised reaction conditions were recruited for the
reduction of assorted nitro substrates (Table 2). Several
aromatic nitro compounds having a variety of substituents
such as –Me, –F, –Cl, –CN, –NH2, and –COOEt (entries 2–9,
Table 2) were conveniently reduced to their corresponding
amines in a high yield. In particular, complex 1 resulted in
nearly quantitative reduction of most of the substrates
and such a fact clearly suggests its catalytic supremacy
over complex 2. The catalysis scope was further extended
to heterocyclic nitro compounds. For example, substrates,
such as 4-nitroimidazole, 5-nitroindole, and 5-nitro-2-amino-
thiazole, were quantitatively reduced to their corresponding
amines (entries 10–12). The reduction of substrates contain-
ing two nitro groups often presents a challenge due to the
observation of incomplete reduction. Satisfyingly, complex 1
selectively and effortlessly reduced both nitro groups in 1,3-
dinitrobenzene, 1,4-dinitrobenzene, and 1,5-dinitronaphthal-
ene (entries 13–15, Table 2). Interestingly, complex 2, on
the other hand, always resulted in incomplete reduction
whereas two products, 1-amino-5-nitronaphthalene (27%) and
1,5-diaminonaphthalene (55%) were obtained in the case of
1,5-dinitronaphthalene.
To evaluate the selectivity of the two catalysts towards sub-
strates offering two delicate functional groups, 3-nitrostyrene
(entry 16) and β-4-dinitrostyrene (entry 17) were employed.19 In
the case of 3-nitrostyrene, 3-nitroethylbenzene was not
observed with both complexes. Such a fact supports a good
control over the chemoselectivity. Interestingly, complex 1 pro-
duced two products: 3-aminostyrene as the major product
(80%) and 3-aminoethylbenzene as the minor one (20%).
A somewhat similar situation was observed with complex 2. It
appears that the formation of 3-aminoethylbenzene is due to
the activation of a double bond by the reduction-generated
–NH2 group. This hypothesis is backed by the fact that both
complexes do not produce 3-nitroethylbenzene at all.
Furthermore, both complexes do not reduce styrene to ethyl-
benzene even with excess hydrazine (entry 20). This hypothesis
is further strengthened by considering the reduction of
β-4-dinitrostyrene having two different types of nitro groups:
one directly attached to the benzene ring while the second one
connected through an ethenyl fragment. The reduction of
β-4-dinitrostyrene afforded two products: 4-(2-aminovinyl)
aniline as the major and 4-(2-nitrovinyl)aniline as the minor
one without affecting the double bond. Collectively, these
results justify that the observation of 3-aminoethylbenzene in
the reduction of β-4-dinitrostyrene was indeed due to the acti-
vation of the double bond and therefore the present catalytic
results exhibit high chemo-selectivity.
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In the literature, there is a dearth of examples, except for a
few nanoparticle-based catalysts, for the reduction of aliphatic
nitro compounds.4b–e,17 Recently, we have shown the hydrazine
mediated reduction of a few aliphatic nitro substrates using tri-
nuclear complexes having catalytically active Co(II) centers.16
To test the catalytic potential of the present Co(III) complexes,
the reduction of a few aliphatic nitro compounds was
attempted. Notably, 1 mol% catalyst loading was not effective
for a reasonable reduction of the aliphatic nitro substrates.
However, on increasing the catalyst loading to 5 mol%,
complex 1 caused nearly quantitative reduction of nitrocyclo-
pentane as well as tert-nitrobutane (96–98%, entries 18 and 19).
As noted with earlier substrates, complex 2 was not quite
effective even with 5 mol% catalyst loading. Notably, both
complexes 1 and 2 were unsuccessful in reducing 3,5-dimethyl-
4-nitrobenzoic acid (entry 21) whereas inconsequential
reduction was noted for 2,6-dimethylnitrobenzene (entry 22).
We believe that the presence of methyl groups on both sides of
a nitro group in these substrates has restricted their access to
interact with the cobalt ion by creating enough steric crowding
(vide infra).
It is important to note that the catalytic results are very
impressive for complex 1 as nearly quantitative reduction was
observed for most of the substrates. On the other hand,
complex 2 did not result in complete reduction in most cases.
Such a fact strongly suggests a significant difference between
the two complexes. Of course, the two complexes differ by
having either electron-withdrawing –Cl groups on the o-phenyl-
ene ring in complex 1 and electron-donating –CH3 substitu-
ents in complex 2. The electrochemical studies have ade-
quately justified the sizable redox difference between the two
complexes. We suggest that the electron-withdrawing –Cl
groups in complex 1 reduce the electron density at the cobalt
center, therefore, de-stabilize the Co3+ state or favour its
reduction to the Co2+ state. In other words, complex 1 is better
suited to activate hydrazine to a large extent when compared
to complex 2. Such a stark difference in the reactivity between
two complexes is significant and illustrates the importance of
judiciously selected substituents in catalyst design.
Mechanistic insights
In order to gain insight into the mechanism of reduction reac-
tion, absorption spectral studies were performed. To first
evaluate whether the present Co3+ complexes, offering a four-
coordinate square-planar geometry, show any tendency to bind
a potential substrate, substrate binding studies were carried
out. For such studies, both complexes 1 and 2 were titrated
with 1-methyl-4-nitrobenzene and aniline as the potential sub-
strate and product, respectively, and the process was moni-
tored spectroscopically. Importantly, both complexes 1 and 2
unambiguously showed the binding of two equivalents of
either 1-methyl-4-nitrobenzene or aniline (Fig. 4 and S10–S12,
ESI†). The binding studies were further analyzed by the linear
regression fitting for 1 : 2 binding between the Co3+ complexes
to that of 1-methyl-4-nitrobenzene and aniline. The binding
constants (K, 10−3 M−2) for 1-methyl-4-nitrobenzene were
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Table 2 Catalytic reduction of assorted nitro compounds using hydrazine in the presence of complexes 1 and 2 as the catalystsa

Yieldb (%)

S. no. Substrate Product 1 2

1 >99 75
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2 >99 54

3 >99 51

4 >99 61

5 99 79

6 >99 89

7 98 42

8 >99 88

9 >99 89

10 >99 87

11 >99 84

12 >99 92

13 >99 83

14 >99 100

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Table 2 (Contd.)

Yieldb (%)

S. no. Substrate Product 1 2

15 0 27
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>99 55

16 0 0

80 54

20 24

17 40 32

60 50

18 98 54

19 96 51

20 0 0

21 0 0

22 12 8

a
Conditions: catalyst: 1 mol%; solvent: MeOH; reducing agent: hydrazine (2 equiv.); temperature: 60 °C, time: 6 h. b Yield was calculated using
the gas chromatograph. c Catalyst: 5 mol%.

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Fig. 5 UV-Vis spectral titration of complex 1 with hydrazine in MeOH;

and change in absorption intensity as a function of equivalents of hydra-
Fig. 4 UV-Vis titration of complex 1 with aniline in MeOH. Top inset:
zine (inset).
Change in absorbance as a function of moles of aniline. Bottom inset:
Linear regression fitting curve for 1 : 2 binding between complex 1 and
aniline.
to pale-brown species, with feature-less absorption spectra,
after one-electron reduction. Fig. 6 presents a controlled poten-
found to be 10.4 and 8.9 for complexes 1 and 2, respectively.20 tial electrolysis experiment for complex 2 that clearly demon-
Similarly, aniline displayed K values (10−3 M−2) of 10.8 and 12.0 strates the reduction of the Co3+ state to Co2+ after the transfer
for complexes 1 and 2, respectively. The binding constants, of one electron (coulomb count: 0.92). In essence, both sub-
although small, justify that both Co3+ complexes are able to strate binding studies and hydrazine based reduction monitor-
bind two equivalents of a potential substrate or a product. ing assert that the present Co3+ complexes 1 and 2 not only
Interestingly, complex 1 illustrated much larger binding affinity bind two equivalents of a substrate but also activate hydrazine
for 1-methyl-4-nitrobenzene when compared to complex 2. Such via a Co3+–Co2+ redox process.
a fact suggests that complex 1 is comparatively more electron More importantly, pale-brown ‘reduced’ species could be
deficient than that of 2, most probably due to the presence of quantitatively oxidized to the original Co3+ complex by
electron-withdrawing substituents and therefore displays larger exposure to molecular oxygen.21 Such a fact is adequately sup-
binding affinity. This in turn supports the better catalytic per- ported by the observation of reversible Co3+/2+ redox couples at
formance of complex 1 in the reduction reactions. fairly negative potentials both for complexes 1 and 2.
We then focussed our attention on the reduction behaviour Importantly, such reversibility is better maintained for
of complexes 1 and 2 towards hydrazine. The reduction reac- complex 1 (Fig. 7) when compared to complex 2 (Fig. S16,
tion was spectroscopically monitored after the incremental ESI†). Such a noteworthy difference between two related
addition of hydrazine to the MeOH solution of Co(III) com-
plexes. The addition of hydrazine to complexes 1 and 2
resulted in an immediate color change from deep purple to
pale brown with disappearance of spectral features at ca. 560
and ca. 740 nm (Fig. 5 and S13, ESI†). Importantly, both spec-
tral titrations established that only 0.25 equivalent of hydra-
zine is required for the complete transformation (see insets of
Fig. 5 and S13, ESI†). It is important to note that one equi-
valent of hydrazine generates 4 electrons and 4 protons before
being converted to N2.17,19 Therefore, the observed stoichio-
metry of one Co(III) complex to that of 0.25 equivalent of hydra-
zine unambiguously confirms that the Co3+ state has been
reduced by one electron to the Co2+ state. Further evidence
came from the cyclic voltammetric experiments that showed
that the incremental addition of hydrazine to a MeOH solution
of 1 or 2 resulted in color change to pale brown accompanied
by the decrease in the current from the metal-based redox Fig. 6 Spectro-electrochemical traces during the coulometric
reduction of complex 2; 2 (black trace) illustrates the original absorption
responses (Fig. S14 and S15, ESI†). Furthermore, controlled spectrum whereas traces A–G (multiple colours) were recorded during
potential electrolysis experiments also resulted in an identical the course of electron transfer. Inset displays the number of electrons
observation wherein deep-purple complexes 1 and 2 changed supplied as a function of current.

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Fig. 7 Recyclability experiment of complex 1 with respect to hydrazine;
original absorption spectrum of complex 1 (black trace A) followed by
reduction with 0.25 equiv. NH2NH2 further followed by oxidation with
O2 (traces B–J). Inset displays subsequent four regenerative cycles.
compounds suggests that while complex 1 maintains its struc-
tural integrity during the hydrazine-based reduction and
oxygen-mediated oxidation; complex 2 is probably not that
stable. In fact, catalytic results are in perfect sync with these
observations. Nevertheless, these experiments established that
the present cobalt complexes function as the redox catalysts
for the hydrazine mediated reduction of nitro substrates.
The hydrazine-mediated reduction typically proceeds in
three steps requiring two-electrons and two-protons at each
step (Scheme 2a). We suggest that two-electrons and two-
Scheme 2 Proposed mechanism for the hydrazine mediated reduction of
nitroaromatics. For simplicity, the case of nitrobenzene has been illustrated.
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protons were provided by two cobalt complexes after the reac-
tion with hydrazine in a step-wise manner (Scheme 2b). Based
on the binding studies, it is proposed that the two substrates
first interact with a Co(III) complex followed by the sequential
electron and proton transfer leading to the product
(Scheme 2c). The reaction involves formation of different inter-
mediates in each step of the catalytic cycle, following either
pathway A or B.17,22 In pathway A, the first step involves the for-
mation of nitrosobenzene which is further reduced to
N-phenylhydroxylamine that ultimately leads to aniline. In
pathway B, nitrosobenzene and N-phenylhydroxylamine
combine to form azoxybenzene that reduces to azobenzene,
then to 1,2-diphenylhydrazine which finally proceeds to
aniline. To identify the intermediate(s) during the reaction,
reduction of nitrobenzene was monitored by UV/Vis spectral
(Fig. S17, ESI†) as well as 1H NMR spectral studies (Fig. S18,
ESI†) at different time intervals. During such a reaction invol-
ving complex 1 as a catalyst, N-phenylhydroxylamine was
detected as an intermediate in the absorption spectrum as
well as 1H NMR spectrum after 2 h. In addition, the generation
of N-phenylhydroxylamine was further confirmed by recording
the high-resolution mass spectrum displaying the M + H+ peak
at 110.0607 (Fig. S19, ESI†). These experiments suggest that
pathway A was operational during the reduction. To further
support pathway A, we performed individual reduction of
nitrosobenzene as well as N-phenylhydroxylamine; both such
reactions quantitatively produced aniline. However, the
reduction of azobenzene as well as 1,2-diphenylhydrazine did
not lead to aniline, therefore, firmly ruling out pathway B.
To further provide a convincing chemical support to the
proposed mechanism (Scheme 2), we attempted the reduction
of 2,2′-dinitrobiphenyl.17b As shown in Scheme 3, 2,2′-dinitro-
biphenyl provides an effective way to trap some of the inter-
mediates being formed during the course of the reaction. With
complex 1, this reaction resulted in the formation of three pro-
ducts: the expected 2,2′-diaminebiphenyl in 44% yield and
benzo[c]cinnoline (20%) as well as benzo[c]cinnoline-5-oxide
(36%). While the formation of 2,2′-diaminebiphenyl was as
anticipated, the other two products justify the intermediacy of
Scheme 3 Hydrazine based reduction of 2,2’-dinitrobiphenyl and its
various products observed during the catalysis.
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‘nitrosobenzene’ and ‘N-phenylhydroxylamine’ during the
reduction reaction which have condensed to produce benzo[c]
cinnoline as well as benzo[c]cinnoline-5-oxide (Scheme 3). It is
worth mentioning that N-phenylhydroxylamine was observed
as an intermediate during the reduction of nitrobenzene both
in UV/Vis spectral (Fig. S17, ESI†) and 1H NMR spectral studies
(cf. Fig. S18, ESI†). On the other hand, complex 2 produced
benzo[c]cinnoline and benzo[c]cinnoline-5-oxide in 40 and
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30% yield respectively, while 2,2′-diaminebiphenyl was pro-
duced in only a 10% yield. The larger proportions of benzo[c]
cinnoline and benzo[c]cinnoline-5-oxide compared to 2,2′-
diaminebiphenyl further justify the inferior nature of complex
2 as a catalyst in the nitro reduction reaction.
Recyclability experiments
We then focused on understanding the potential recyclability
of complexes 1 and 2 in catalysis. For such a purpose, two
experiments were performed. In the first experiment, a fixed
amount of complex 1 (1 mol%) was taken in a reaction flask
while fresh batches of para-CNPhNO2 (1 equiv.) and hydrazine
(2 equiv.) were added. Importantly, under these conditions,
complex 1 was successful in reducing several batches of para-
CNPhNO2 with only ca. 5% drop in performance in the fifth
cycle (Fig. S20, ESI†). In the second experiment, the solvent
was removed from the reaction mixture followed by the
addition of ethyl acetate which allowed the isolation of the
catalyst. The recovered complex 1 was then used in the next
catalytic run without any further purification and/or regener-
ation. The same strategy was repeated for five consecutive runs
(Fig. S21, ESI†). In such an experiment, approximately 2–4%
loss in activity per catalytic run was noted which suggests that
a part of the complex may have decomposed during every cata-
lytic cycle in addition to loss in recovery. Furthermore, at the
end of the 2nd cycle, recovered complexes 1 and 2 were charac-
terized by the FTIR spectra (Fig. S22 and S23, ESI†) as well as
by the X-ray powder diffraction (XRPD) studies (Fig. S24 and
S25, ESI†). While complex 1 displayed an excellent match to
that of the as-synthesized sample, recovered complex 2 did
show certain differences particularly in the XRPD pattern.
Such a fact justifies the recyclability experiments (using
NH2NH2 and O2) suggesting the limited stability of complex 2
and therefore its inferior catalytic performance.
Experimental
Materials and methods
All reagents were obtained from commercial sources and used
as received. Solvents were dried and/or purified using standard
literature methods.23 (Et4N)2[CoCl4] salt was synthesized
according to a literature method.24 Ligands H4L1 and H4L2
were synthesized according to our earlier report.9a
(Et4N)[CoL1] (1). Ligand H4L1 (0.10 g, 0.275 mmol) was dis-
solved in 5 mL DMF and treated with solid NaH (0.026 g,
1.101 mmol) under the dinitrogen atmosphere. The mixture
was stirred until H2 evolution ceased (ca. 10 min). This
332 | Inorg. Chem. Front., 2017, 4, 324–335
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Inorganic Chemistry Frontiers
mixture was added to a solution of (Et4N)2[CoCl4] (0.127 g,
0.275 mmol) in 5 mL DMF under an inert atmosphere. The
resulting mixture was further stirred for 1 h under an O2
atmosphere at room temperature which resulted in a dark
purple solution. This solution was filtered through a pad of
celite in a medium porosity frit. The solvent was removed
under reduced pressure and the crude product was isolated
after washing repeatedly with diethyl ether. Vapor diffusion of
diethyl ether to a MeCN solution of the crude product at room
temperature afforded a crystalline product within 2–3 d. Yield:
0.098 g (64%). Anal. Calcd for C24H28N5O2Cl2Co (548.35):
C 52.57, H 5.15, N 12.77; Found C 52.18, H 5.35, N 12.78. FTIR
spectrum (Zn–Se ATR, cm−1): 2990, 2927, 1605, 1595, 1537,
1457, 1001, 747. Conductivity (DMF, ca. 1 mM solution, 298 K):
ΛM = 85 Ω−1 cm2 mol−1. UV/Vis spectrum [λmax, nm (ε, M−1 cm−1),
MeOH]: 742 (260), 560 (700), 495 (sh, 520). UV/Vis spectrum
[λmax, nm (ε, M−1 cm−1), CH3CN]: 810 (sh, 250), 689 (sh, 330),
545 (780), 487 (sh, 620), 383 (1000). UV/Vis spectrum [λmax,
nm (ε, M−1 cm−1), DMF]: 833 (sh, 250), 678 (sh, 370),
546 (860), 489 (sh, 690), 384 (1150). MS (ESI−): m/z calcd for
[C16H8Cl2N4O2Co]− 416.9356, found 416.9375.
(Et4N)[CoL2] (2). This complex was synthesized in an identi-
cal manner as that of 1 using following reagents: H4L2 (0.10 g,
0.310 mmol), NaH (0.029 g, 1.240 mmol), (Et4N)2[CoCl4]
(0.143 g, 0.310 mmol). Yield: 0.094 g (60%). Anal. Calcd for
C26H36N5O3Co (including 1H2O as observed in microanalysis
data, 525.52): C 59.42, H 6.90, N 13.33; Found C 58.98, H 6.88,
N 13.20. FTIR spectrum (Zn–Se ATR, cm−1): 3378, 2987,
2945, 1663, 1608, 1592, 1548, 1478, 1444, 1390, 1000, 747.
Conductivity (DMF, ca. 1 mM solution, 298 K): ΛM = 80
Ω−1 cm2 mol−1. UV/Vis spectrum [λmax, nm (ε, M−1 cm−1),
MeOH]: 744 (185), 561 (480), 499 (sh, 370). UV/Vis spectrum
[λmax, nm (ε, M−1 cm−1), CH3CN]: 927 (sh, 210), 828 (sh, 255),
689 (sh, 360), 554 (660), 474 (sh, 480), 392 (sh, 740). UV/Vis
spectrum [λmax, nm (ε, M−1 cm−1), DMF]: 929 (sh, 250), 834
(sh, 330), 680 (sh, 450), 559 (860), 480 (sh, 660), 393 (1010). MS
(ESI−): m/z calcd for [C24H12Cl2N4O2Co]− 377.044; Found 377.039.
Procedure for reduction of nitro substrates
In a Schlenk reaction flask, the nitro substrate (1.0 mmol) was
taken in MeOH (2 ml) and the catalyst (1 mol%) was added.
The content was stirred for 5 min followed by the addition of
hydrazine monohydrate (2.0 mmol) under inert conditions.
The reaction mixture was stirred at 60 °C for 6 h while progress
of the reaction was monitored by the gas chromatograph (GC).
After completion, the reaction mixture was passed through a
plug of 100–200 mesh silica and concentrated to afford the
organic product(s). The product(s) was identified and/or
characterized by the GC, GC-MS, and 1H NMR spectra wher-
ever required.
Characterization data for a few representative products
Aniline. 1H NMR (400 MHz, CDCl3): δ 7.26–7.19 (m, 6H),
6.83 (t, J = 7.9 Hz, 3H), 6.73 (d, J = 8.0 Hz, 6H), 3.62 (s, 7H).
13
C NMR (100 MHz, CDCl3): δ 146.76 (C1), 129.54 (C2), 118.69
(C3), 115.37 (C4).
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Inorganic Chemistry Frontiers
4-Chloroaniline. 1H NMR (400 MHz, CDCl3): δ 7.09 (d, J =
8.6 Hz, 1H), 6.59 (d, J = 8.5 Hz, 1H), 3.54 (s, 1H). 13C NMR
(100 MHz, CDCl3): δ 144.92 (C1), 129.21 (C3), 123.21 (C4),
116.35 (C2).
4-Iodoaniline. 1H NMR (400 MHz, CDCl3): δ 7.40 (d, J =
8.8 Hz, 1H), 6.45 (d, J = 8.6 Hz, 1H). 13C NMR (100 MHz,
CDCl3): δ 139.07 (C4), 129.42 (C2), 120.07 (C3), 114.80 (C1).
Ethyl-4-aminobenzoate. 1H NMR (400 MHz, CDCl3): δ 7.84
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(d, J = 8.3 Hz, 4H), 6.62 (d, J = 8.5 Hz, 4H), 4.30 (q, J = 7.1 Hz,
4H), 3.96 (s, 3H), 1.35 (t, J = 7.3 Hz, 6H). 13C NMR (100 MHz,
CDCl3): δ 166.87 (s), 150.78 (s), 131.65 (s), 120.17 (s), 113.88 (s),
60.45 (s), 14.52 (s).
3-Nitroaniline. 1H NMR (400 MHz, CDCl3): δ 7.57 (d, J =
8.2 Hz, 1H), 7.49 (s, 1H), 7.28 (d, J = 8.2 Hz, 1H), 6.94 (d, J =
8.0 Hz, 1H), 3.98 (s, 2H). 13C NMR (1001 MHz, CDCl3):
δ 149.28 (C1), 147.57 (C5), 130.02 (C3), 120.78 (C2), 113.20
(C4), 109.09 (C6).
4-Nitroaniline. 1H NMR (400 MHz, CDCl3): δ 7.91 (d, J =
9.1 Hz, 1H), 6.69 (s, 1H), 6.56 (d, J = 9.1 Hz, 1H). 13C NMR
(100 MHz, CDCl3): δ 156.22 (C1), 136.13 (C4), 126.93 (C3),
112.89 (C4).
1,3-Phenylenediamine. 1H NMR (400 MHz, CDCl3): δ 6.94
(t, J = 7.9 Hz, 2H), 6.11 (d, J = 7.8 Hz, 4H), 6.02 (s, 2H), 3.45
(s, 9H). 13C NMR (100 MHz, CDCl3): δ 147.60 (C1), 130.31 (C3),
106.09 (C2), 102.04 (C4).
1,4-Phenylenediamine. 1H NMR (400 MHz, CDCl3): δ 6.56
(s, 4H), 3.31 (s, 4H). 13C NMR (100 MHz, CDCl3): δ 138.66 (C1),
116.83 (C2).
Physical measurements
The conductivity measurements were done in DMF using the
digital conductivity bridge from the Popular Traders, India
(model number: PT-825). The elemental analysis data were
obtained from the Elementar Analysensystem GmbH Vario EL-III
instrument. The NMR measurements were done using a Jeol
(400 MHz) instrument. The infra-red spectra (either as KBr pellet
or Zn–Se ATR) were recorded using either Perkin-Elmer FTIR
2000 or Spectrum-Two spectrometers. The absorption spectra
were recorded using the Perkin-Elmer Lambda-25 spectrophoto-
meter. The cyclic voltammetric experiments were performed
using a CH Instruments electrochemical analyzer (model
1120A). The cell contained a glassy-carbon electrode, a Pt wire
auxiliary electrode, and Ag+/Ag as the reference electrode.25 The
solutions were ca. 1 mM in the complex and ca. 0.1 M in the sup-
porting electrolyte, TBAP.25 Gas chromatographic experiments
were carried out with the Perkin Elmer Clarus 580 with an Elite-
5 column. The variable-temperature magnetic susceptibility
measurements were performed by using the PPMS (Cryogenics
Ltd, USA) at 0.5 Tesla applied magnetic field and having a closed
cycle based cryogen free system. The susceptibilities were cor-
rected for diamagnetic corrections by using literature values.26
Crystallography
Single crystals suitable for the X-ray diffraction studies were
grown by the vapor diffusion of diethyl ether to a MeCN solu-
tion of complex 1. Intensity data were collected on an Oxford
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Research Article
CCD diffractometer having an Xcalibur sapphire diffraction
measurement device at 293(2) K using graphite-mono-
chromated Mo-Kα radiation (λ = 0.71073 Å).27 The empirical
absorption correction was applied using the spherical harmo-
nics implemented in the SCALE3 ABSPACK scaling algo-
rithm.27 The structure was solved by the direct methods using
SIR-92 28 and refined by full-matrix least-squares refinement
techniques on F2 using SHELXL97.29 All calculations were
done using the Wingx crystallographic package.30 The
crystallographic data collection and structure solution para-
meters are presented in Table S1 (ESI†).
Conclusions
This work has discussed the synthesis and characterization of
two square-planar Co(III) complexes supported with pyrrole-
carboxamide ligands. Both complexes were successfully used
in the catalytic reduction of assorted nitro compounds encom-
passing aromatic, heterocyclic, and even aliphatic substrates.
Binding studies asserted that four-coordinated Co(III) com-
plexes bind two equivalents of nitro substrates. The absorption
spectral titrations established that the mechanism involved
redox shuttling between Co3+ and Co2+ states adequately sup-
ported by the electrochemical studies. Out of the two com-
plexes, the one with electron-withdrawing substituents
resulted in nearly quantitative reduction for most of the sub-
strates. Such a fact has been related to better stabilization of
the Co2+ state and therefore better activation of hydrazine.
These results illustrate the significance of well-defined coordi-
nation complexes in delineating a challenging reaction and
future work is directed to explore similar complexes in other
noteworthy organic reactions.
Acknowledgements
RG acknowledges the financial support from the Council of
Scientific & Industrial Research (CSIR), New Delhi and the
University of Delhi. Authors thank the CIF-USIC of this
university for the instrumental facilities including X-ray data
collection and AIRF of JNU, New Delhi for the magnetic
measurements. SK thanks CSIR for the RA fellowship.
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Inorganic Chemistry Frontiers
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by the addition of excess TBAP. Such a sequence did not
allow the regeneration of original Co3+ species by O2
mediated oxidation.
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