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Abnormal N-Heterocyclic Carbene Based Nickel Complex for

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Catalytic Reduction of Nitroarenes

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a a
Gonela Vijaykumar and Swadhin K. Mandal*
Herein we report the synthesis of anickel(II) dichloro complex bearing an abnormal N-heterocyclic carbene (aNHC) salt,
1,3-bis(2,6-diisopropylphenyl)-2,4-diphenylimidazolium. The NiCl2(aNHC)2 complex has been used as an efficient catalyst
for the reduction of nitroarenes with hydrosilanes to give aromatic amines in good to excellent yields. This catalytic
protocol can tolerate functional groups such as halide, alkene or nitrile. Furthermore, the longevity of catalyst was tested
in successive catalytic cycles, which indicates a sustained catalytic activity over multiple catalytic cycles.

nitro compounds with high catalyst loading.14 Beller and co-

Introduction
The synthesis of anilines or amines from the corresponding
nitro compounds is an important process, which finds
application in a variety of agrochemicals, dyes, natural
1
products, and biologically active compounds. Amines can be
prepared by a number of methods including substitution
reactions, rearrangements, ammonolysis, reductions etc.
Reduction by catalytic hydrogenation is usually the most
efficient and general method to produce aromatic amines.2
Typical hydrogenation process requires stoichiometric
3 4
reductants such as metal based catalysts (zinc, tin, copper,
5 best of our knowledge, very recently Quan, Wang and co-
etc.) or strong acid medium, hazardous molecular hydrogen
and high-pressure reactors. In addition to catalytic
hydrogenations, the reduction of nitroarenes in the presence
of several reducing agents such as CO/H2O, sodium
6 using abnormal N-heterocyclic carbene based copper
hydrosulfite,
7
tin(II) chloride,
8
NaBH4,
9
hydrosilanes,
10
hydrazine
11
and ammonia borane
12
have been studied.
Moreover, hydrogenation of aromatic nitro compounds poses
chemoselectivity problems, particularly for those containing
other reducible groups such as halide, nitrile or alkene. Among
the reported methods, hydrosilylation has been considered as
the safest in order to avoid the necessity to use autoclaves
13
and/or to handle hydrogen gas. Until now, only a limited
reports are found in the literature based on nitroarene
reduction to anilines using silanes. For example, in 2010,
Mirza-Aghayan and co-workers have investigated the
efficiency of Et3SiH–PdCl2 system for the reduction of aromatic
workers reported iron catalysed reaction with silanes for
selective reduction of nitroarenes to anilines at refluxing
temperature.15 Park and co-workers have also reported a
hydrosilylation system using Au nanoparticles catalysts with
16
silanes under low catalyst loading. Later on, many reports
appeared on hydrosilylation of nitroarenes with metal-based
17 18 19 20
catalysts (Pt, Rh, Sn, and Re ). However, relatively long
reaction times, high temperature and/or the toxicity of costly
metals are drawbacks of these protocols.
Surprisingly, until recently nickel mediated hydrosilylation
of nitro compounds into anilines has not been reported. To the
workers observed the reduction of nitro-compounds with
21
Ni(acac)2 using PMHS. On the basis of our recent report on
the chemoselective hydrosilylation of carbonyl compounds
22
catalyst, as well as a part of our interest to develop catalyst
23
with isolated abnormal NHC, we became interested in the
development of convenient and efficient hydrosilylation
protocol for nitroarenes using inexpensive nickel catalyst.
Herein, we report a nickel(II) chloride complex (1; Scheme 1)
as a catalyst, which is supported by an abnormal N-
heterocyclic carbene for hydrosilylation of aromatic nitro
compounds. This nickel catalyst showed good chemoselectivity
in the presence of various reducible functional groups such as
halide, alkene or nitrile. Furthermore, the longevity of catalyst
was successfully tested in successive catalytic cycles indicating
a sustained catalytic activity of the present catalyst.

Results and discussion

We chose abnormal N-heterocyclic carbene as the ligand of

choice for the synthesis of nickel complex 1. Complex 1 was
isolated as a red solid in good yield from the treatment of the

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DOI: 10.1039/C6DT00470A
ARTICLE Journal Name

aNHC salt (IA) with potassium bis-(trimethylsilyl)amide and
nickel(II) chloride in dry THF. During the reaction, the colour of
the reaction mixture changes from colourless to red.
Analytically pure compound of 1 was obtained by
recrystallization of the dried reaction mixture from toluene at -
20 oC, after 2 days yielding dark red crystals of 1 in nearly 70%
yield. The complex 1 was characterized by NMR spectroscopy,
1
X-ray crystallography and elemental analysis. The H NMR
spectrum of the reaction mixture featured absence of the
bond lengths were found to be 1.9444(19) Å and 2.1935(5) Å,
respectively. These values compare well with those observed
in a related normal NHC nickel (II) complex, NiCl2(IiPr) [1.933(6)
Å, 2.167(3) Å and 2.172(3) Å for Ni-C, Ni-Cl1 and Ni-Cl2,
24
respectively]. The C1-Ni-Cl1 and C1-Ni1-C1 bond angles were
determined as 91.92(6)° and 180.00° indicating a nearly
perfect square planar geometry around the Ni(II) centre in
complex 1.

Dalton Transactions Accepted Manuscript

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characteristic singlet at δ 8.8 ppm arising from C-5(H) of Table 1 Evaluation of different silanes, solvents, time and
[a]
imidazolium salt IA, which confirms the carbene binding to temperature for the reduction of 4-nitrotoluene.
nickel centre. The C-5 carbon resonance bound to the nickel
13
centre appeared at δ 155.5 ppm in the C NMR spectrum of 1. NO 2
Catalyst 1 (5 mol%) NH2
This NMR chemical shift value is comparable to that reported + Silane
i
Solvent, temp, time
for normal N-heterocyclic carbene nickel complex NiCl2(I Pr)
i
(I Pr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), where
a metal-bound carbene carbon appeared at δ 168.4 ppm in the
13
C NMR spectrum.
24 Entry Catalyst Silane Solvent Temp Time Yield
o [b]
(2 equiv) ( C) (h) (%)

1 1 PhSiH3 THF 60 1 99
2 1 Ph2SiH2 THF 60 1 85
3 1 Ph3SiH THF 60 3 NR
Ph Ph
H N
4 1 PMHS THF 60 3 33
Cl
Ph NiCl2 N N 5 1 Et3SiH THF 60 3 5
Ni 6 1 (EtO)3SiH THF 60 10 75
Ph N N
KN(SiMe3)2 Ph N Cl Ph 7 1 (MeO)3SiH THF 60 3 8
THF, rt, 12h 8 1 Cl3SiH THF 60 3 68
9 1 PhSiH3 Toluene 100 3 52
HCl.Cl 10 1 PhSiH3 DMSO 150 3 48
IA 1 11 1 PhSiH3 DCM 40 12 14
12[c] 1 PhSiH3 Dioxane 90 3 78
13 - PhSiH3 THF 60 10 NR
Scheme 1 Synthesis of complex 1 14 NiCl2 PhSiH3 THF 60 10 NR
a
Typical conditions: catalyst 1 (5 mol %), 1 mmol 4-
nitrotoluene, 2 equiv. silane,c 5 mL THF, 60 oC. b Isolated
yield after chromatography. No catalyst.

As a part of our ongoing interest to develop aNHC based

Fig. 1. Perspective ORTEP view of the molecular structure of 1. Hydrogen
atoms have been omitted for the sake of clarity. Selected bond lengths (Å)
and bond angles (°): Ni1-C1, 1.9444(19); Ni1-Cl1, 2.1935(5); C1-Ni1-C1,
180.0; C1-Ni1-Cl1, 91.92(6), Cl1-Ni1-Cl1 179.999(11).
Finally, the molecular structure of 1 was determined by the
X-ray crystallographic study (see Figure 1), which confirmed
the atom connectivity of 1 as depicted in Scheme 1.
Compound 1 crystallizes in the triclinic space group P-1. The
geometry around the nickel ion is square planar exhibiting the
abnormal mode of NHC binding in 1. The Ni1-C1 and Ni-Cl1
homogeneous catalysts for different organic transformations,
we first evaluated the catalytic activity of 1 for the
hydrosilylation of aromatic nitro compounds. The study begins
with an optimization of the operating conditions on a model
reaction involving 4-nitrotoluene with different silanes,
temperature, solvents and time. The full conversion of the
desired product was observed with primary silane (PhSiH3) in
o
THF at 60 C within 1 h (Table 1, entry 1). Secondary silane
(Ph2SiH2) also works quite efficiently (Table 1, entry 2). When
polymethylhydrosiloxane (PMHS) was used as silane, it
resulted in less activity (33% yield, Table 1, entry 4).
Alkylsilanes and alkoxysilane (Et3SiH, (EtO)3SiH and (MeO)3SiH)
containing only one Si–H group gave poorer results (Table 1,
entries 5, 6 and 7). The hydrosilylation of 4-nitrotoluene when
performed with Ph3SiH, no catalysis was observed. Different
solvents were also evaluated. The reaction was slower when
performed in toluene, DMSO and dichloromethane (Table 1,
entries 9-12). Obviously, no reaction takes place without
catalyst (Table 1, entry 13) and with NiCl2 (Table 1, entry 14).

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[a]
Table 2 Scope of the hydrosilylation of nitroarenes to anilines. From this study, it was observed that phenylsilane is the most
Catalyst 1 (5 mol%) effective silane for this particular catalytic system to produce
R 1 NO2 + PhSiH3 R1 NH2 the corresponding anilines (Table 1, entry 1). We tested this
THF, 60 o C, 1h
combination for a number of aryl and heteroaryl nitro
Entr y Sub st ra te R Prod uct
[b]
Yie ld (% ) substrates successfully leading to nearly quantitative isolated
yield of the anilines (Table 2). Nitrobenzene as well as nitro
1 H 98 benzene attached with electron donating groups at the para-
2 F 85 position furnished the corresponding aniline products (Table 2,
3 Cl 89 entries 1, 6, and 7). Also nitroarenes containing electron
98
withdrawing substituents (Cl, Br, F, I, CN), in the ortho-, meta-,
4 NO2 Br NH2

Dalton Transactions Accepted Manuscript

or para- positions provided their corresponding anilines in very
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5 I 97 good yields. Notable is the chemoselective reduction of the

R R
6 OMe 99 nitro group in the presence of halides (without
7 NH2 dehalogenation), cyano and C=C bond substituents. When
98
nitroarenes were substituted with a halogen (Cl, Br, F, I; Table
2, entries 2-5, 8-10, 12, and 13), no dehalogenated product
8 Cl 79 was observed in comparison to hydrogenation in classical
25
NO2 NH2 conditions with palladium on charcoal. Interestingly, there is
9 Br 97
no significant difference observed in activity among all ortho-,
10 I 93 meta- and para-substituted nitroarene under similar
R R conditions. When the nitroarene was substituted with a nitrile
11 CN 94
(Table 2, entry 11), only the nitro function was reduced to
amine. For this particular substrate, this method is selective in
12 NO2 F NH2 26
98 comparison to the hydrogenation using platinum catalyst.
13 R Br 97 Surprisingly, reduction of nitro arene bearing alkene functional
R
group resulted in the corresponding amine without any by
NO2 NH2 products (Table 2, entry 15). This nitro group reduction is
14 important since Beller previously reported that FeBr2/PPh3 was
96 15
not a good catalyst for the reduction of 3-nitrostyrene.
However, nitro substituent on the hetero ring showed a
OH OH
decreased reactivity yielding the corresponding anilines (Table
NO2 NH2
2, entries 17-19). Then we were interested to test the
92 reduction of an arene containing two nitro groups. In the case
15
of the 1,4-dinitrobenzene and 1,3-dinitrobenzene (Table 2,
entries 20 and 21), we observed only one nitro group was
NO 2 NH2
reduced to amine with 2 eq. PhSiH3. However, complete
98 reduction of both nitro groups occurred by 4 equiv. of PhSiH3
16
in 2 h. Analytical data of the prepared compounds were
NO2 NH2 compared to those reported in the literature (see ESI).
N N Furthermore, we assessed the longevity of catalyst 1 by
17 78 performing several catalytic runs into the same reaction pot to
check whether the catalyst remains active for several catalytic
cycles. We have carried out 5 successive catalytic runs by using
N N 5 mol% of catalyst. After every 1 h interval, we added a fresh
18 66 batch of substrates (4-nitrotoluene and phenylsilane) without
NO2 NH2
adding any additional catalyst into the reaction vessel. After
O O each 1 h interval, we checked the substrate consumption by
1
19 84 recording the H NMR spectrum of the reaction mixture after
1
O NO2 O NH2 initial workup. The H NMR spectrum indicates a complete
consumption of substrates within 1 h time for three successive
NO2 NH2 catalytic runs (see Figure 2) indicating no loss of catalytic
[c,d] 85 activity. After three catalytic cycles, the catalytic activity slowly
20
O2N H 2N reduces. The overall isolated yield of 4-toluedine after five
consecutive cycles was 78% (TON 78). This result clearly
NO2 NH2
[c,d]
demonstrates that the catalyst stays active for three
21 64
consecutive catalytic runs.
NO 2 NH2

a
Reaction conditions: 5 mol% catalyst 1, nitroarene (1 mmol),
b
phenylsilane (2 mmol) and 5 mL dry THF. Isolated yield after
c d
column chromatography. 4 mmol phenylsilane was added. t = 2 h.

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ARTICLE
100
80
Conversion (%) a
60
40
20
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0
1 2 3 4
Number of catalytic runs
Figure 2. Longevity of the catalyst 1 was tested by monitoring the time
required for complete consumption of substrate by 1H NMR
spectroscopy in five consecutive catalytic cycles. Reaction condition: 5
mol% catalyst 1, 4-nitrotoluene (1 mmol), phenylsilane (2 mmol) and 5
mL dry THF. After completion of each catalytic cycle, fresh 4-
nitrotoluene (1 mmol) and phenylsilane (2 mmol) were added and no
additional catalyst was added. a Conversion was determined for each
cycle after 1 h by 1H NMR spectrum of reaction mixture.
To understand the mechanistic cycle, we have performed a
series of stoichiometric reactions with catalyst 1. The reaction
between complex 1 and nitrobenzene in a 1:1 ratio in THF
1 29
showed no change in the H NMR spectrum, which is
suggestive of no direct reaction between catalyst 1 and
nitrobenzene (see Figure S45, ESI). However, the reaction
between complex 1 and PhSiH3 in a 1:1 ratio in THF revealed a
1
sharp change in the H NMR spectrum indicating a reaction
between 1 and PhSiH3. The Si-H resonance shifted towards a
deshielded region as compared to the free PhSiH3 from δ 4.23
13
to 4.95 ppm. Moreover, the C NMR spectrum of this reaction
mixture clearly indicated a peak at δ 155.5 ppm, which is
indicative of the intact Ni-carbon (carbene) attachment (see
29
Figure S46, ESI). Additionally, the Si NMR spectrum of this
reaction mixture displayed a singlet at δ -36.3 ppm (see Figure
S47, ESI) with a clear shift from the free PhSiH3 (at δ -59.8
1
ppm). However, the H NMR spectrum of the reaction mixture
did not show any peak, which can be assigned to the Ni-H
resonance. This observation suggests the formation of a Ni-
silyl complex by reaction between catalyst 1 and PhSiH3, as
also noted recently by Shimada and co-workers in the case of
27
nickel catalysed hydrosilylation of alkenes. However, our all
attempts to isolate this compound in the pure form by
crystallization have been unsuccessful.
Conclusions
Herein, we report synthesis of a square planar nickel complex
bearing an abnormal N-heterocyclic carbene. This nickel
complex is an efficient catalyst for hydrosilylation of
nitroarenes into the corresponding amines leading to nearly
quantitative yield with chemoselectivity. The catalyst
remained active for three successive catalytic runs without any
loss of its activity. The present procedure is an appealing
inexpensive and convenient methodology for the preparation
of anilines.
4 | J. Name., 2012, 00, 1-3
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Experimental section
General methods and instrumentation
All manipulations were performed under a dry and oxygen free
atmosphere (argon) using standard Schlenk techniques or
inside a glovebox maintained at below 0.1 ppm of O2 and H2O
o
levels, utilizing oven-dried (130 C) glassware after evacuation
while hot prior to use. All solvents were distilled from
Na/benzophenone prior to use. All other chemicals were
Dalton Transactions Accepted Manuscript
purchased from Sigma–Aldrich and used as received.
Elemental analysis was performed in a Perkin–Elmer 2400,
5 Series II, CHNS/O analyser. The melting point was measured in
a sealed glass tube on a Büchi B-540 melting point apparatus.
Analytical TLC was performed on a Merck 60 F254 silica gel
plate (0.25 mm thickness). NMR spectra were recorded on a
JEOL ECS400 MHz spectrometer and on a Bruker Avance III 500
MHz spectrometer. All chemical shifts were reported in ppm
using tetramethylsilane as a reference. Chemical shifts (δ)
downfield from the reference standard were assigned positive
values. Abnormal N-heterocyclic carbene salt (1,3-bis(2,6-
diisopropylphenyl)-2,4-diphenyl-imidazolium salt, IA, Scheme
1) was prepared starting from N,N’-bis(2,6-
28
diisopropylphenyl)benzamidine following a modified
literature protocol.
Synthesis of Complex 1
Under an argon atmosphere, THF (10 mL) was added at -78 C
o
to a mixture of 1,3-bis(2,6-diisopropylphenyl)-2,4-
diphenylimidazolium salt IA (308 mg, 0.50 mmol), nickel(II)
chloride (64.8 mg, 0.5 mmol) and potassium
bis(trimethylsilyl)amide (200 mg, 1 mmol). After 30 min at -78
o
C, the mixture was warmed to room temperature and stirred
for 12 h. Solvent was evaporated under reduced pressure and
the residue was extracted with toluene (20 mL). Analytically
pure dark red crystals of the title compound were obtained by
o
recrystallization from same solvent at -20 C. Yield: 423 mg
◦ 1
(0.35 mmol, 70%); mp 265–268 C; H NMR (400 MHz, CDCl3,
o
25 C, TMS): δ 8.53 (d, J = 7.5 Hz, 2H), 7.67 (t, J = 8 Hz, 2H),
7.31 (m, 4H), 7.18 (m, 2H), 6.81 (t, J = 7.5 Hz, 2H), 6.66 (d, J =
7.5 Hz, 2H), 6.40 (d, J = 7.5 Hz, 2H), 3.21–3.14 (m, 2H), 2.50–
2.43 (m, 2 H), 1.34 (d, J = 7 Hz,6 H), 0.81 (d, J = 7 Hz, 6H), 0.79
13
(d, J = 7 Hz, 6H), 0.47 (d, J = 7 Hz, 6H) ppm; C NMR (100 MHz,
o
CDCl3, 25 C, TMS): δ 155, 144.4, 144.3, 139.8, 138.0, 137.1,
134.4, 131.1, 130.9, 129.9, 129.3, 127.8, 127.7, 124.5, 124.4,
124.1, 123.8, 122.5, 28.9, 28.6, 28.6, 25.3, 24.4, 23.1, 22.9,
22.8; Elemental analysis: Anal. Calcd for C78H88Cl2N4Ni: C,
77.35; H, 7.32; N, 4.63. Found: C, 76.08; H, 7.43; N, 4.85.
X-ray Crystallographic Details
Single crystal of the complex 1 was mounted on a glass pip.
Intensity data were collected on a Super Nova, Dual, Mo at
zero, Eos diffractometer. The crystal was kept at 100 K during
data collection. Atomic coordinates, isotropic and anisotropic
displacement parameters of all non-hydrogen atoms were
30
refined using Olex2 and the structure was solved with the
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31
Superflip structure solution program using Charge Flipping
32
and refined with the ShelXL refinement package using Least
Squares minimization. CCDC number 1451179 contains the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
General Procedure for the Hydrosilylation of Nitroarenes
In an oven-dried Schlenk flask, complex 1 (0.005 mmol, 5
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mol%), 2 mmol PhSiH3 (248µL) and 1 mmol of the appropriate
nitroarene in dry THF (2 mL) were added together. The mixture
o 5. A. Saha and B. C. Ranu, J. Org. Chem. 2008, 73, 6867–6870.
was stirred for 1 hour in a preheated oil bath at 60 C. The
reaction was monitored by TLC. After consumption of the
starting material, the reaction mixture was opened to the air
and MeOH (1 mL) was added followed by aqueous NaOH (2 M,
2 mL). The resulting mixture was stirred for 1 h and
subsequently extracted with DCM (3 × 30 mL). The organic
phase was concentrated in vacuum, and the purity of the
1 3, 69.
residue was checked by H NMR spectroscopy. Flash
chromatography (a mixture of EtOAc and petroleum ether was
used as the eluent, and the ratio of EtOAc to petroleum ether
was adjusted accordingly) was performed unless the crude
product was estimated to be greater than 95% pure.
Procedure for Catalyst Longevity Experiment
In a Schlenk flask, the complex 1 (5 mol%), phenylsilane (2
mmol) and 4-nitrotoluene (1 mmol) were taken and stirred at
o 1
60 C. The reaction mixture was monitored by H NMR
spectroscopy by taking aliquots of the reaction mixture after 1
h intervals and the reaction was stopped when the
consumption of substrates got complete. Again a fresh batch
of substrates phenylsilane (2 mmol) and 4-nitrotoluene (1
mmol) were added for the next catalytic cycle without adding
any further catalyst into the reaction vessel. This procedure
was repeated for a total of five consecutive catalytic runs.
Acknowledgements
We thank SERB (DST), India (Grant No. SR/S1/IC-25/2012) for
financial support. GVK is thankful to UGC, New Delhi for
research fellowship.
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ARTICLE
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