Article

pubs.acs.org/JPCC

Chiral Ni-Schiff Base Complexes inside Zeolite‑Y and Their

Application in Asymmetric Henry Reaction: Effect of Initial Activation
with Microwave Irradiation
Mukesh Sharma,† Biraj Das,† Galla V. Karunakar,‡ Lanka Satyanarayana,§ and Kusum K. Bania*
†
Department of Chemical Sciences, Tezpur University, Tezpur, Assam 784028, India
‡
Division of Crop Protection Chemicals and §Center for NMR and Structural Chemistry, Indian Institute of Chemical Technology,
Uppal Road, Tarnaka, Hyderabad, Telangana 500007, India
*
S Supporting Information
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ABSTRACT: Chiral Ni(II)-Schiff base complexes synthesized inside the

cavity of zeolite-Y were used as heterogeneous chiral catalyst for
asymmetric Henry reaction. Synthesized catalysts were characterized
using various spectrochemical and physicochemical techniques. Solid state
NMR analysis has been used to confirm the internal location of the metal
complexes. To the best of our knowledge MAS NMR has not been used to
characterize chiral diamagnetic Ni2+-Schiff base complex inside zeolite-Y.
The catalytic activities of the materials were dependent on temperature,
solvent, and amount of catalyst. High catalytic transformation of aldehydes
with nitromethane to nitro-aldol product (92% yield and 83% ee, S-
isomer) was achieved at −10 °C. Initial activation of the reaction with
microwave irradiation for 15 min leads to a substantial decrease in the
reaction time in comparison to normal stirring. Heterogeneous catalysts
were found to be advantageous over the homogeneous counterparts in terms of recyclability of the catalyst. Most importantly,
product selectivity, percentage yield, and enantioselectivity were found to be high with the heterogeneous catalyst. The catalytic
activities of the metal complexes were influenced by the structural modification of the Schiff base ligands. Calculation of the
energy barrier using density functional theory (DFT) suggests that the activation barrier is less in the case of the encapsulated
complexes.

■ INTRODUCTION
Asymmetric Henry reaction or nitro-aldol condensation
reaction has been considered as an important class of organic
transformations due to the application of the aldol product in
various natural product syntheses.1−5 Different homogeneous
and heterogeneous chiral catalysts are implemented to achieve
such asymmetric transformation.6−10 Although various chiral
homogeneous catalysts so far reported have been found to
show good catalytic activity, but they fail in terms of
recyclability, and in many cases homogeneous catalysts suffer
from loss of catalytic activity.11−14 Nowadays, many researchers
use different techniques, such as use of ionic liquids,
supercritical liquids, etc., to recover the homogeneous chiral
catalyst.15 However, besides these methodologies, heterogeni-
zation of homogeneous catalyst via encapsulation or immobi-
lization into solid support has been found to be advantageous
over various other techniques.16−18 Zeolites, MCM-41, etc. and
such inorganic mantles are nowadays found to be excellent
supports for heterogenization of homogeneous catalysts.19−22
Out of the various Si-based materials, zeolite-Y, a crystalline
aluminosilicate with pore dimension of 7.4 Å and supercage of
13 Å, has been found to be the most effective host for
encapsulation of transition metal complexes. Starting from the
pioneering work of Herron,23 quite a good number of works
have been reported on encapsulation of transition metal
complexes inside the cavity of zeolite-Y. From our group we
have reported design of various metal complexes with 1,10
phenanthroline, with picolinates, and with chiral and achiral
Schiff base complexes inside zeolite-Y.24−28 Although a
significant number of metal catalyst has been synthesized
inside the zeolite-Y cavity, significantly fewer reports are
available on designing of chiral catalyst inside zeolite-Y.
Recently, we have reported the synthesis of a chiral vanadium
Schiff base complex inside zeolite-Y29 and also a Cu-
Cinchonidine complex supported on zeolite-Y.30 Vanadium
Schiff base complexes were found to be efficient catalysts for
oxidation of 2-naphthol and styrene. Looking into the
advantages of zeolite-Y encapsulated chiral metal Schiff base
complexes, in this study we report the synthesis and
characterization of the Ni2+-Schiff base complexes inside
zeolite-Y and their application in asymmetric Henry reaction.
Received: April 5, 2016
Revised: June 8, 2016
Published: June 8, 2016

© 2016 American Chemical Society 13563 DOI: 10.1021/acs.jpcc.6b03457

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Scheme 1. Structures of Ligands (a) L1, (b) L2, (c) L3, and (d) L4; (e−h) Structures of Corresponding Nickel Complexes; and
(i−l) Schematic Representation of Zeolite-Y Encapsulated Metal Complexes
■ EXPERIMENTAL SECTION
Materials. Nickel(II) chloride dihydrate, NiCl2·2H2O,
procured from SRL, was used as a source of nickel.
Salicylaldehyde and chiral 1,2-diamines used for synthesis of
chiral Schiff base ligands were purchased from Alfa Aesar and
Sigma-Aldrich, respectively. Tetrabutyl ammonium bromide
(TBAB) of analytical grade (AR), used as electrolyte in cyclic
voltammetry analysis, was obtained from E-Merck. NaY zeolite
was purchased from Sigma-Aldrich. Aldehydes used for
asymmetric Henry reaction were purchased from Sigma-
Aldrich. All the solvents used during the synthesis of materials
and in asymmetric Henry reactions were purified by standard
procedures prior to their use.
Preparation of Schiff Base Ligands. Details of the
synthesis of four Schiff base ligands, namely L1, L4, L3, and L4,
are provided in the Supporting Information along with their 1H
and 13C NMR data (Figures S1−Figure S4). The structures of
the four ligands are shown in Scheme 1.
Synthesis of the Ni2+-Schiff Base Complexes. To a
solution of Schiff base ligands prepared in 5 mL of acetonitrile
(CH3CN), an equimolar solutions of NiCl2·H2O (dissolved in
DMF) was added dropwise. The resultant clear reddish-brown
solution was stirred for 6 h and was left for recrystallization.
Dark brown red crystals were obtained after 6 days which were
then washed with methanol. The neat Ni-Schiff base complexes
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herein are designated as Ni2+-L1, Ni2+-L2, Ni2+-L3, and Ni2+-L4
(Scheme 1).
Synthesis of Ni2+-Exchanged Zeolite, Ni2+-Y. Ni2+
exchanged zeolite was prepared by heating Na-Y zeolite in air
at a rate of 1 K min−1 and by further heating for 24 h at 773 K
to remove the impurities. One gram of Zeolite-Y was dissolved
in a round-bottom flask with 50 mL of 0.01 M aqueous solution
of NiCl2·2H2O, and the resultant mixture was stirred for 24 h at
room temperature. To prevent metal hydroxide preparation,
the pH of the solution was maintained between 3 and 5. After
24 h, the solutions were filter by using Whatman No. 1 filter
paper and were washed thoroughly with warm deionized water
to remove all dissolved chloride ions or until receipt of a
negative test with AgNO3. The Ni2+ exchanged zeolite was then
dried for 15 h in an oven at 373 K for further use.
Synthesis of Zeolite-Y Encapsulated Ni(II)-Schiff Base
Complexes. Zeolite-Y supported vanadium Schiff base
complexes were synthesized following the “Ship in a bottle”
synthesis method.29 In a general procedure, to the Ni2+@NaY
chiral 1,2 diammine and 2-hydroxybenzaldehyde or its dervative
in either case dissolved in DMF were added in stoichiometric
amount and reflux at 40 °C for 32 h under nitrogen
atmosphere. The light brownish powders so obtained were
subjected to Soxhlet extraction for several hours using
acetonitrile, ethanol, and diethyl ether as solvents. The color
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Table 1. BET and CHN Analysis of NaY, Ni2+-L1@NaY, Ni2+-L2@NaY, Ni2+-L3@NaY, and Ni2+-L4@NaYa
NLDFT BJH Elemental Analysis (%)
Ni2+-Loading (mg/ NLDFT PSD Vmicro BJH pore size Pore volume BET surface area
Compound 100 mg) (Å) (cm3/g) (Å) (cm3/g) (m2/g) C H N
NaY - 6.2 0.36 6.2 0.30 645 - - -
Ni2+-L1@NaY 15.26(14.45) 3.2 0.14 2.9 0.12 248 63.03 5.82 7.35
Ni2+-L2@NaY 10.15(10.32) 2.8 0.11 2.7 0.09 256 62.02 5.20 7.23
Ni2+-L3@NaY 14.70(14.89) 2.9 0.16 3.4 0.18 356 63.84 5.48 7.11
Ni2+-L4@NaY 12.90 (12.68) 3.0 0.13 3.0 0.15 318 60.83 5.89 6.17
a
% Ni2+ loading is calculated from ICP analysis. % Ni2+ loading values obtained from AAS are shown in parentheses.

of the samples did not change after Soxhlet extraction and

prolonged exposure to air, indicating the formation of metal
complexes inside zeolite-Y. The powders were then dried under
vacuum and kept for 32 h in a desiccator for further
characterization. Synthesized zeolite supported metal com-
plexes are represented herein as Ni2+-L1@NaY, Ni2+-L2@NaY,
Ni2+-L3@NaY, and Ni2+-L4@NaY (Scheme 1).
General Procedure for Asymmetric Henry Reaction. In
a mixed solvent of acetonitrile and ethanol 15 mg of the (Ni-L1
or Ni2+-L1@NaY) catalyst was dissolved followed by addition
of 4-nitrobenzaldehyde (5 mmol) in a typical round-bottom
flask used for microwave treatment. The resulting mixture was
stirred for a few minutes, and nitromethane (5 mmol) was
added dropwise into it. The whole reaction mixture was then
subjected to mirowave irradiation with 50% power (425 W) at
31 °C for 15 min in a scientific multimode microwave reactor Figure 2. PXRD patterns of (a) NaY, (b) Ni2+-Y, and (c) zeolite-Y
equipped with a digital power and temperature control unit. encapsulated Ni2+-Schiff base complexes.
After irradiation with microwave, the reaction mixture was
magnetically stirred for 5 h at −10 °C. Product formation was
confirmed by checking the progress of the reaction using TLC.
Resultant nito-aldol produt was separated by washing the
reaction mixture several times with a 9:2 mixture of hexane/
ethyl acetate solution. Heterogeneous catalyst was recovered by
simple filtration and completely dried under vacuum and stored
in a desiccator for further use.
Physical Measurements and Computational Details.
Details of the physical measurements and different character-
ization techniques used in this study are given in the
Supporting Informations along with the methods we
implemented for the density functional theory (DFT)
calculations using the DMOL3 program.31

■ RESULTS AND DISCUSSION

The synthesized chiral Ni2+ Schiff base complexes were
characterized via various spectrochemical and physicochemical

Figure 3. FTIR spectrum of (a) Ni2+-L1 complex, (b) Ni2+-L2

complex, (c) Ni2+-L3 complex, and (d) Ni2+-L4 complex.

analyses prior to application in asymmetric catalysis. Zeolite-Y

encapsulated complexes were initially characterized by perform-
ing the elemental analyses. The results of the elemental analyses
are presented in Table 1. The Si/Al ratio in zeolite-Y was found
to be ∼2.5, consistent with the previously reported values.29
The amounts of metal content in the encapsulated system were
found to be less than those of the nickel exchanged zeolite-Y,
Figure 1. BET isotherms for zeolite-Y encapsulated complexes: (a) Ni2+@NaY, due to participation of Ni2+ ion in the formation of
Ni2+-L1@NaY, (b) Ni2+-L2@NaY, (c) Ni2+-L3@NaY, and (d) Ni2+- metal Schiff base complex inside zeolite-Y. The carbon (C),
L4@NaY. hydrogen (H), and nitrogen (N) contents in the encapsulated
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Figure 4. FTIR spectra of (a) NaY, (b) Ni2+-L1@NaY, (c) Ni2+-L2@NaY, (d) Ni2+-L3@NaY, and (e) Ni2+-L4@NaY.
complexes were found to be consistent with the expected
molecular formula of the Ni2+ Schiff base complexes. In
particular, the C/N ratios in all the encapsulated Ni2+-Schiff
base complexes were found to be approximately the same as
that in the neat complexes.
BET surface area analysis was conducted to determine the
surface area of the encapsulated complexes. The corresponding
adsorption/desorption isotherms for the four encapsulated
complexes are comparatively shown in Figure 1, and the surface
area and pore dimension values are given in Table 1 along with
elemental analysis. The patterns of the adsorption/desorption
isotherms for all the complexes were found to be more or less
identical. However, there exists a significant difference in the
surface area, pore size, and pore volume among the
encapsulated systems. Apart from Barret−Joyner−Halenda
(BJH) modeling, the pore size distribution (PSD) was also
obtained from the adsorption branch using the non-local
density functional theory (NLDFT), assuming a cylindrical
pore shape. The PSD was determined via a NLDFT model
using nitrogen adsorption data.32−34 The BJH and NLDFT
micropore PSDs were almost found to be comparable. In all the
encapsulated complexes, the pore size, pore volume, and BET
surface area were found to be significantly less in comparison to
those for neat NaY (Table 1). A decrease in the surface area
and pore volumes of the parent NaY clearly indicates the
presence of a metal complex inside the cavity of zeolite-Y.28 It is
pertinent to mention that the surface area reported herein for
NaY zeolite is taken from our previously reported results.29
The PXRD patterns of Na-Y and Ni2+-NaY and the
encapsulated complexes are shown in Figure 2. The PXRD
patterns of the Na-Y and Ni2+-NaY were almost similar (Figure
2a and 2b, respectively). However, in the case of encapsulated
complexes, the intensities of the I220 and I311 planes observed at
10° and 12° 2θ values became reversed (Figure 2c). In the case
of Na-Y and Ni2+-NaY, the intensity of the 220 plane was
greater than that of the 311 plane; that is, I220 > I311. Reversal of
the intensities of the 220 and 311 planes, i.e. I220 < I311,
completely reveals the formation of Ni2+-Schiff base complex
inside zeolite-Y.35,36 Such observations of the reversal of the
peak intensities in the zeolite-Y encapsulated complexes were
also made previously by various other researchers. We also
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observed such changes in case of Cu2+ and V(IV) Schiff base
complexes incorporated inside zeolite-Y.28,29
The FTIR spectra of all four neat Ni2+-Schiff base complexes
shown in Figure 3(a−d) exhibited the characteristic CN,
CC, and C−O stretching vibrations in the regions 1600−
1625, 1440−1540, and 1380−1382 cm−1, respectively. The
presence of these bands, characteristic of ligand, duly confirms
the formation of the metal Schiff-base complexes, NiL1, NiL2,
NiL3, and NiL4. The FT-IR spectrum of zeolite-Y (NaY)
shown in Figure 4a shows a strong broad band at 1000 cm−1
due to the asymmetric stretching vibration of (Si/Al)O4 units.37
The broad bands at 1650 and 3500 cm−1 are due to lattice
water molecules and the surface hydroxylic group. Na-Y zeolite
also shows characteristic bands at 463, 713, 786, 1021, and
1130 cm−1 (Figure 4a), and these bands were not modified on
encapsulation of the Ni-Schiff base complexes, indicating
encapsulation has not affected the zeolite framework (Figure
4(b−e)). In the zeolite-Y encapsulated complexes, we obtained
a similar vibrational band as in the neat Ni-Schiff-base
complexes. In the usual case, NaY-zeolite or Ni2+@NaY did
not show any bands in the region of 1200−1600 cm−1. The
presence of a band between 1200 and 1600 cm−1 (Figure 4) in
the encapsulated complexes also gives an indication of the
formation of Ni2+-L1@NaY, Ni2+-L2@NaY, Ni2+-L3@NaY, and
Ni2+-L4@NaY.
In recent years, solid state NMR (MAS NMR) has found
wide application in solid state chemistry and material science.
27
Al and 29Si -MAS NMR has been used to characterize zeolite-
Y or such zeolite type materials.30 However, to the best of our
knowledge, MAS NMR has not been well explored in analyzing
zeolite-Y encapsulated complexes. One reason for less
application of MAS NMR in such host guest chemistry might
be due to the paramagnetic nature of the maximum number of
metal complexes incorporated inside NaY. However, nowadays,
paramagnetic MAS NMR is finding application in predicting
the structures of paramagnetic metal complexes. Ishii and co-
workers38 have extensively used the technique in determining
the structure of paramagnetic Cu complexes. We have recently
studied the adsorption of cinchonidine in the Cu2+-exchanged
zeolite-Y.30
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Figure 5. Solid state 13C NMR of (a) Ni2+-L1@NaY and (b) Ni2+-L2@NaY.
The Ni2+-Schiff base complexes synthesized herein are
diamagnetic, having highly symmetric square planar geometry.
Since the complexes are diamagnetic, therefore we used MAS
NMR to predict the formation of the metal complexes inside
the zeolite-Y. 13C NMR of the zeolite-Y complexes shows signal
characteristics of the Schiff base ligands (Figure 5 and Figure
6). Slight up- and downfield shifts of the δ values in ppm are
due to the steric impartment imposed by the zeolite matrix.
Thus, MAS NMR analysis of the zeolite-Y encapsulated
complexes confirmed the formation of the metal complexes
inside zeolite-Y.
From TGA analysis it was found that all the four neat Ni2+-
Schiff base complexes have two sharp degradations in the
ranges 335−380 °C and 390−430 °C due to decomposition of
the ligands (Figure 7(a−d)). Variation in the thermal
degradation can be attributed to the slight variation in the
structural backbone of the metal complexes. More than 10%
weight loss is observed in the range 335−380 °C while more
than 40% weight loss occurs above 390 °C. Initial
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decomposition below 100 °C may be attributed to the solvent
molecule or some solvated water molecule. But in the case of
zeolite encapsulated Ni2+‑L@NaY complexes, no such decom-
position occurs in the region between 300 and 450 °C, which
indicates the enhanced stability of Ni2+-Schiff base complexes
after encapsulation 7(e−h).
The synthesized materials were also characterized by UV−
vis/DRS spectroscopy and cyclic voltammetry studies. The
outcomes of these analyses are given in detail in the Supporting
Information (Figures S5−S8). The assignments of the
electronic transitions (Table S1) involved in the synthesized
Ni2+-Schiff base complexes were supported by the reported
results.39,40 Shifting of the absorption spectra and changes in
the redox potential values (Figures S7 and S8) further
confirmed the successful encapsulation of the Ni-Schiff base
complexes inside the cavity of the zeolite-Y.
After characterization of material, the Ni-Schiff base
complexes were used as catalysts for transforming asymmetric
Henry reactions. Chiral metal−Schiff base complexes are
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Figure 6. Solid state 13C NMR spectra of (a) Ni2+-L3@NaY and (b) Ni2+-L4@NaY.

Table 2. Nitroaldol Reaction of 4-Nitrobenzaldehyde

Catalyzed by Ni2+-L1 and Ni2+-L1@NaY in Different
Solvents at Room Temperature
Ni2+-L1 Ni2+-L1@NaY
Solvent Time (h) % Yield % ee % Yield % ee
Toluene 48 - - - -
Cyclohexane 48 - - - -
DCM 48 27 17 27 20
Chloroform 48 24 25 28 28
Acetonitrile 48 28 30 26 32
Acetonitrile/DCM 48 35 45 38 43
Chloroform/acetonitrile 48 38 42 40 42
Ethanol 48 22 26 25 26
Figure 7. TGA analysis of (a) Ni2+-L1, (b) Ni2+-L2, (c) Ni2+-L3, (d) Methanol 48 20 27 23 28
Ni2+-L4, (e) Ni2+-L1@NaY, (f) Ni2+-L2@NaY, (g) Ni2+-L3@NaY, and Ethanol/acetonitrile 48 46 40 48 46
(h) Ni2+-L4@NaY.
our group has explored the catalytic activity of such metal Schiff
known to catalyze various asymmetric organic transformations. base complexes. We have been successful in synthesizing both
Starting from the Jacobsen, Mn-Schiff base complexes, chiral- homogeneous and heterogeneous Cu, Fe, Mn, and V-Schiff
Schiff base complexes have been extensively used for the base complexes.24−30,39 Cu- Schiff base complexes, particularly,
production of various fine chemicals.41,42 For the past few years were found to be excellent chiral catalysts for asymmetric
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Table 3. Effect of Temperature on Nitro-Aldol Reaction of 4-Nitrobenzaldehyde Taken As Case Study Using Ni2+-L1 and Ni2+-
L1@NaY Catalystsa
Ni-L1 Ni-L1@NaY
Entry Tempr (°C) Solvent Time (h) % Yield % ee Major isomer % Yield % ee Major isomer
1 0 C2H5OH/CH3CN 5 70 56 S 54 60 S
2 −5 C2H5OH/CH3CN 5 80 58 S 64 65 S
3 −10 C2H5OH/CH3CN 5 86 74 S 92 83 S
4 −20 C2H5OH/CH3CN 5 72 68 S 66 58 S
5 −30 C2H5OH/CH3CN 5 64 55 S 64 55 S
6 −40 C2H5OH/CH3CN 5 57 46 S 57 46 S
a
All the reactions were carried out after irradiating with microwave for 15 min.

Table 4. Results of the Henry Reaction with Various Table 5. Results of the Henry Reaction in the Presence of
Aldehydes in the Presence of Various Homogeneous Various Zeolite-Y Encapsulated Ni2+-Schiff Base Complexes
Catalystsa at −10 °Ca

Ni2+-L1 Ni2+-L2 Ni2+-L3 Ni2+-L4 Ni2+-L1@ Ni2+-L2@ Ni2+-L3@ Ni2+-L4′@

NaY NaY NaY NaY
% % % % % % % %
Reactant product Yield ee Yield ee Yield ee Yield ee % % % % % % % %
Reactant product Yield ee Yield ee Yield ee Yield ee
1a 2a 81 69 76 65 75 63 60 58
1b 2b 86 74 80 69 78 67 73 64 1a 2a 89 78 84 71 78 67 75 68
1c 2c 84 68 73 66 72 65 61 56 1b 2b 92 83 86 75 81 72 78 70
1d 2d 80 65 77 63 74 61 60 53 1c 2c 91 77 81 70 79 68 71 67
1e 2e 79 67 74 61 71 63 57 51 1d 2d 87 78 83 72 78 71 72 64
1f 2f 82 69 75 65 65 60 62 54 1e 2e 89 80 84 74 75 73 70 65
a 1f 2f 86 79 80 71 73 70 69 63
Reactions are conducted at 5 mmol scale employing 5 equiv of a
nitromethane in ethanol. Reactions are carried out at −10 °C using 15 Reactions are conducted at 5 mmol scale employing 5 equiv of
mg of the catalyst. The % ee (S-isomer) values are calculated from nitromethane in ethanol. Reactions are carried out at −10 °C using 15
HPLC analysis. All the reactions were carried out after irradiating with mg of the catalyst. The % ee (S-isomer) values are calculated from
microwave for 15 min. HPLC analysis. All the reactions were carried out after irradiating with
microwave for 15 min.
Henry reaction.24,28 Thus, with our little experience in
asymmetric Henry reaction, we herein analyzed the catalytic
activity of the synthesized Ni-Schiff base complexes. In this
study, we also studied the effect of microwave irradiation on the
catalytic performance.
To study the catalytic ability of the metal Schiff base
complex, initially we took 5 mmol of 4-nitrobenzaldehyde (4-
NB) as a test substrate and reacted it with 5 mmol of
nitromethane (CH3NO2) in the presence of Ni-L1 and Ni2+-
L1@NaY at room temperature using acetonitrile as solvent.
The results of the Henry reaction obtained at room
temperature were not satisfactory (Table 2). We could isolate
only 28% of the product with 30% ee (S-isomer major) using
Ni-L1 catalyst and 26% and 32% ee (S-isomer major) using
Ni2+-L1@NaY catalyst. From our previous experience, we have Figure 8. PXRD analysis of the recovered catalyst Ni2+-L1@NaY after
seen that the Henry reaction is highly dependent on the nature the (a) 5th, (b) 6th, and (c) 7th cycles.
of the solvent, on temperature, and also on the amount of
catalyst. So we carried out the reaction in different solvents at
room temperature. It was found that polar solvents give better ethanol and acetonitrile. Therefore, an ethanol/acetonitrile
results than nonpolar solvents. The results of the Henry mixture was taken as a suitable solvent system. At room
reaction performed in different solvents are given in Table 2. temperature, the % yield and % ee were not so significant and
The reaction was found to give better yield (48%) and also the reaction time was high. Thus, in order to reduce the
enantioselectivity (46%) when the solvent was a mixture of time and also to obtain better yield and % ee, we performed the
13569 DOI: 10.1021/acs.jpcc.6b03457
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Scheme 2. Schematic Representation of the Intermediates
(Int-I and Int-II) That May Form during the Catalytic
Reaction
nitro-aldol reaction using the same substrates under microwave
conditions and at variable temperature. Before monitoring the
reaction at variable temperature, we first studied whether the
reaction proceeds under microwave conditions or not. In recent
years researchers have taken advantage of microwave
irradiation, as under such conditions reactions complete within
a short interval of time and with better yields than with
conventional methods.43−45 There are various reactions
reported which are being transformed very efficiently using
microwave irradiation within a short period of time. However,
reports on performing asymmetric Henry reactions using
microwave conditions are sparse. To observe the effect of
microwave irradiation, we again consider 4-NB and CH3NO2 as
the test substrate. The interesting thing to observe was that
when we irradiate the reaction mixture with both catalysts (Ni-
L1 or Ni2+-L1@NaY) for 5 min and then for 15 min, we did
not observed the formation of the product. But the reaction
Figure 9. Optimized geometries of the metal complexes and the plausible intermediate states that may form during the catalytic reaction in the
presence of Ni2+-L1 and Ni2+-L2 catalyst.
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mixture (which was initially irradiated for 15 min), when
subjected to magnetic stirring at room temperature in a mixed
solvent of ethanol and acetonitrile, produced nitro-aldol
product with the same yield and % ee within 5 h of stirring.
Thus, on microwave irradiation, the reaction time was reduced
from 48 to 5 h. The role of microwave irradiation is not totally
understood. Probably, initial activation of the reaction in the
presence of nickel catalysts proceeded very slowly, so it
required a longer period of time in the absence of microwave
irradiation. On microwave irradiation, the molecule gets initial
excitation, consequently leading to a decrease in activation
energy, thereby favoring the reaction to occur at a faster rate.46
Although microwave assisted catalytic reaction reduced the
time of completion, it has not enhanced the % yield and % ee.
Thus, in order to obtain better yield and enantioselectivity, we
again carried out the reaction at variable temperature with 4-
nitrobenzaldehyde as the test substrate. In doing so, we first
activated the reaction system with microwave irradiation and
then subjected it immediately to magnetic stirring in a low
temperature reaction bath. The results obtained at different
temperatures are given in Table 3. From Table 3 it can be
observed that, at −10 °C and activating the reaction mixture
initially with microwave irradiation, the product yield and % ee
were found to be the highest. This was an unusual effect of
microwave irradiation followed by simultaneous cooling on the
reaction time, % yield, and % ee. Further, the zeolite-Y
encapsulated Ni-Schiff base complex shows better catalytic
activity in comparison to the homogeneous counterpart.
Heterogeneous Ni2+-L1@NaY catalyst gives almost 92% yield
with 83% ee (S-isomer major) while the homogeneous Ni2+-L1
gives 86% with 74% ee (S-isomer major) under similar reaction
conditions.
The amount of catalyst was also found to affect the catalytic
performance. Initially we varied the catalyst amount from 5 mg
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Figure 10. Optimized geometries of (a) Ni2+-L1@NaY, (b) Ni2+-L1@NaY+ CH2NO2 (Int-1), (c) Ni2+-L2@NaY, and (d) Ni2+-L2@NaY+ CH2NO2
(Int-1).
to 25 mg. When 5 mg was used with Ni-L1, the product yield
was found to be 78% (with 4-nitrobenzaldehyde and nitro-
methane as the substrate) with 66% ee (S-isomer major). But at
15 mg, the yield was found to be maximum. Increasing the
amount of catalyst up to 25 mg did not lead to any substantial
change in the catalytic activity. Hence, we consider the 15 mg
of the catalyst as the optimum catalytic amount. After
optimizing the solvent, the temperature, and the catalytic
amount, we then carried out the nitro-aldol reaction using all
other catalysts. Since the time required for nitro-aldol product
formation significantly decreased on activating the reaction
mixture with microwave irradiation for 15 min, therefore we
performed all the reactions using different substrates and
different catalysts following the same method, i.e. microwave
irradiation (15 min) followed by magnetic stirring at −10 °C.
The results of the Henry reaction using various homogeneous
and heterogeneous catalysts are given in Table 4 and Table 5,
respectively. In the presence of Ni exchanged zeolite-Y, Ni2+@
NaY, the catalytic results were very poor, which indicates that
chiral Schiff base is required to bring about the effective
asymmetric Henry reaction. Ni2+-L1@NaY catalyst was found
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to give better catalytic activity than the other homogeneous and
heterogeneous chiral catalysts.
Since chiral catalysts are costly, it is always important to
determine a suitable technique to recycle those catalysts. To
test the recyclability of the chiral catalyst, we again considered
Ni2+-L1 and Ni2+-L1@NaY as test catalysts. Homogeneous
Ni2+-Schiff base catalyst Ni2+-L1 could not be recycled;
however, we could use the heterogeneous chiral catalyst Ni2+-
L1@NaY for four consecutive cycles without any loss in the
catalytic activity. However, after the fourth cycle there was a
subsequent decrease in the catalytic activity. The catalytic
results in the fifth, sixth, and seventh runs are given in Table S2.
In order to understand the reason behind the loss in catalytic
activity, we again recorded PXRD of the catalyst after the fifth,
sixth, and seventh runs. The PXRD patterns were found to be
different from those of the initial catalyst, and some additional
peaks were observed between 5° and 10° 2θ value due to
degradation of the chiral catalyst (Figure 8). This truly explains
the reason behind the loss of catalytic activity after the fourth
cycle.
DOI: 10.1021/acs.jpcc.6b03457
J. Phys. Chem. C 2016, 120, 13563−13573
The Journal of Physical Chemistry C
From our experimental studies we found that the catalytic
activities of the Ni-Schiff base complexes were influenced by the
slight variation in the ligand structure. The Schiff base complex
with the phenyl groups shows superior activity in comparison
to the Schiff base complex having a cyclohexane ring. In order
to determine the reason behind the difference in catalytic
activities of the metal complexes, we performed some density
functional theory (DFT) calculations using the DMOL3
program.31 We optimized the four complexes and also the
possible intermediate states that may be involved during the
catalytic nitro-aldol reaction. The reaction may proceed
through the formation of two intermediates, one via the attack
of nitronate ion to the metal complex, forming intermediate I
(Scheme 2), and the second by the attack of I to the aldehyde
moiety, forming intermediate II (Scheme 2). The optimized
geometries of the complexes and intermediates are shown in
Figure 9 and Figure 10. From energy calculations it was evident
that the energy required for the formation of intermediate I in
the cases of Ni2+-L1 and Ni2+-L2 complexes is 14.7 and 15.16
kcal/mol, respectively. While the same for those of Ni2+-L3 and
Ni2+-L4 complexes is 16.4 and 19.1 kcal/mol. On going from
intermediate states I to II, Ni2+-L1 and Ni2+-L2 have to cross a
barrier of 6.4 and 6.9 kcal/mol while the other two complexes
require 10.4 and 12.2 kcal/mol, respectively. Thus, from our
theoretical calculation it is evident in the case of Schiff base
complexes with the phenyl ring that the energy barrier is less
while in case of the complexes with the cyclohexane ring the
energy barrier is slightly higher. These differences in the
activation energy barrier bring significant difference in the
catalytic activity of the metal complexes.
We also optimized the metal complexes and also the first
intermediate state for the encapsulated systems using the
DMOl3 program. The structures of the metal complexes and
the intermediate state I for all the four complexes are shown in
Figures 9 and 10 and Figures S9−S10 (in the Supporting
Information). Since the first step, i.e. the attack of the nitronate
ion to the metal center, is believed to be the rate-determining
step, therefore we have optimized only the intermediate state I
to compare the reactivity of the metal complexes. From our
DFT-based calculations it was found that the energy required
for the formation of intermediate I in the case of Ni2+-L1@NaY
and Ni2+-L2@NaY complexes is 10.6 and 11.4 kcal/mol,
respectively. While the same for those of Ni2+-L3@NaY and
Ni 2+ -L4@NaY complexes is 14.4 and 15.8 kcal/mol,
respectively. Thus, this indicates that the energy barrier is
further lowered on encapsulation, leading to the high reactivity
of the encapsulated nickel Schiff base complexes in comparison
to the neat complexes.
■
CONCLUSIONS
In summary we can conclude that four different Ni-Schiff base
complexes has been successfully encapsulated inside the cavity
of zeolite-Y and were well characterized. Solid state NMR
analysis has been used for the first time to characterize the
zeolite-Y encapsulated Ni-Schiff base complexes. The synthe-
sized Ni-Schiff base complexes usually do not show good
catalytic activity. However, on initiation with microwave
irradiation followed by magnetic stirring at cold conditions,
better catalytic activity is shown. Under these reaction
conditions, the catalysts were found to act as excellent catalysts
for asymmetric Henry reaction, giving 92% yield and 83% ee
(S-isomer major). Density functional theory calculation justifies
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the reason behind the higher catalytic activity of the
heterogeneous catalyst over its homogeneous counterparts.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b03457.
Procedure for synthesis of ligands, physical measure-
ments, UV−visible assignments, cyclic voltammetry
analysis, 13C NMR of ligands, results of recyclability,
and optimized geometries of encapsulated complexes and
intermediates (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: kusum@tezu.ernet.in or bania.kusum8@gmail.com.
Phone: 09859929360.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
KKB and MS thank Science and Engineering Research Board,
(SERB), Department of Science and Technology (DST), India,
for the financial grant (NO SB/EMEQ-463/2014).
■
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