Cu(ii) anchored nitrogen-rich covalent imine network (CuII-CIN-1): An efficient and recyclable heterogeneous catalyst for the synthesis of organoselenides from aryl boronic acids in a green solvent

Article abstract of DOI:10.1039/c4ra08909j

A new heterogeneous copper catalyst has been synthesized by immobilizing Cu(ii) onto the surface of a nitrogen rich porous covalent imine network material CIN-1 and it was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), EDAX, X-ray photoelectron spectroscopy (XPS), N₂ adsorption-desorption, UV-vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric (TGA), and EPR spectroscopic analyses. The material has been successfully used to catalyze the cross-coupling reaction between aryl boronic acids and diphenyldiselenide to synthesize unsymmetrical organoselenides. Due to its high surface area and highly accessible catalytic sites, it shows good to excellent catalytic activity for the C-Se bond forming reaction, which was evident from the high TOF of the catalyst in this reaction. The catalyst was recycled for six repetitive runs without any appreciable loss of catalytic activity suggesting its potential usefulness in C-Se bond forming reaction. This journal is

Full text of DOI:10.1039/c4ra08909j

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Cu(II) anchored nitrogen-rich covalent imine
II
network (Cu -CIN-1): an efficient and recyclable
Cite this: RSC Adv., 2014, 4, 46075
heterogeneous catalyst for the synthesis of
organoselenides from aryl boronic acids in a green
solvent†
a
b
c
a
c
Susmita Roy,‡ Tanmay Chatterjee,‡ Biplab Banerjee, Noor Salam, Asim Bhaumik*
and Sk Manirul Islam*a
A new heterogeneous copper catalyst has been synthesized by immobilizing Cu(II) onto the surface of a
nitrogen rich porous covalent imine network material CIN-1 and it was characterized by powder X-ray
diffraction (XRD), transmission electron microscopy (TEM), EDAX, X-ray photoelectron spectroscopy
2
(XPS), N adsorption–desorption, UV-vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR),
thermogravimetric (TGA), and EPR spectroscopic analyses. The material has been successfully used to
catalyze the cross-coupling reaction between aryl boronic acids and diphenyldiselenide to synthesize
unsymmetrical organoselenides. Due to its high surface area and highly accessible catalytic sites, it
shows good to excellent catalytic activity for the C–Se bond forming reaction, which was evident from
the high TOF of the catalyst in this reaction. The catalyst was recycled for six repetitive runs without any
appreciable loss of catalytic activity suggesting its potential usefulness in C–Se bond forming reaction.
Received 19th August 2014
Accepted 8th September 2014
DOI: 10.1039/c4ra08909j
www.rsc.org/advances
7
multifaceted functionalities inside the framework. Synthesis of
these functionalized porous materials is a very fast growing eld
Introduction
Covalent organic frameworks (COFs) which possess either 2D or of research as they have diverse applications in many frontline
D polymeric structures with permanent porosity, are generally areas of energy, environment and biomedical research. Incor-
3
formed via covalent linkage between various organic moieties poration of nitrogen containing functional groups on the
1
and these are widely explored as gas storage materials.
A
surface of porous materials oen enhances their stability and
bottom-up chemistry approach has been employed extensively catalytic activity. Jiang and co-worker have showed that nitrogen
to design similar types of microporous organic polymers like dopped carbon nanotubes (CNTs) can act as an excellent
2
polymers of intrinsic microporosity (PIMs), conjugated micro- support for metal nanoparticles, which exhibited much better
3
4
porous polymers (CMPs) or porous organic polymers (POPs).
catalytic activity than pristine CNTs for the Heck cross-coupling
8
These materials have found extensive application as heteroge- reaction between iodobenzene and styrene. Nitrogen rich
neous catalysis for the synthesis of value added ne chemicals.
5
covalent triazine framework and magnetic nanomaterials graf-
The pore size and the surface area of the nanoporous materials ted mesoporous polyaniline have been utilized as efficient
9
are largely depended on the molecular length of the building catalytic supports. Recently we have developed a nitrogen rich
6
blocks and the synthesis conditions. Further, these porous porous covalent imine networkmaterial CIN-1 through the
materials can be suitably modied through the incorporation of Schiff-base condensation reaction between 1,4-piper-
azinedicarbaldehyde and melamine, which was then used as
efficient support for palladium to catalyze C–C cross-coupling
a
Department of Chemistry, University of Kalyani, Nadia, 741235, West Bengal, India.
10
reactions. With our continued interest in this eld, now we
have graed copper at the surface of CIN-1 and explored its
catalytic activity for the synthesis of a wide range of carbon-
E-mail: manir65@rediffmail.com; Fax: +91-33-2582-8282; Tel: +91-33-2582-8750
b
Department of Organic Chemistry, Indian Association for the Cultivation of Science,
Kolkata-700032, India
c
Department of Material Science, Indian Association for the Cultivation of Science, heteroatom (C–Se) bond forming reaction.
Kolkata-700032, India. E-mail: msab@iacs.res.in; Fax: +91-33-2473-2805; Tel: +91-
Carbon–selenium bond forming reactions are of continued
interest because of the synthesis of highly potent organo-
selenium compounds in biomedical research. These
compounds possess antiviral, antimicrobial, antioxidant, anti-
3
3-2473-4971
†
Electronic supplementary information (ESI) available: Details of
II
1
13
characterisation (FTIR) of CIN-1 and Cu -CIN-1, H NMR and C NMR spectral
data of all products listed in Table 2. See DOI: 10.1039/c4ra08909j
11
hypertensive, antitumor and anticancer activities. They also
‡
These authors contributed equally.
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II
Scheme 1 Cu -CIN-1 catalyzed phenyl selenylation of aryl boronic
acids.
1
2
have important applications as catalysts
and material
13
science. Hence several methods have been developed for the
synthesis of organoselenium compounds. Various transition
14
15
16
17
metals like Pd, Ni, Fe and Cu were employed to catalyze
the C–Se bond forming reactions of aryl halides/boronic acids
and selenol/PhSeNa/diphenyldiselenide for the synthesis of
organoselenides. Among the various selenylating reagents,
diphenyldiselenide is used because of its relatively higher
stability and less toxicity. Synthesis of organoselenides from
aryl halides is well-explored compared to boronic acids. Few
II
Fig. 1 XRD analysis of Cu -CIN-1 material.
TEM analysis
TEM images of the as-synthesized CIN-1 material as well as for
the Cu -CIN-1 material are shown in Fig. 2(a) and (b), respec-
tively. There are some dark spots (shown in red circles) for the
Cu -CIN-1 Fig. 2(b) material throughout the specimen grid,
which can be attributed to the presence of Cu in the polymer
framework. The EDX pattern of the Cu -CIN-1 material is shown
II
17b,e–g,i,n
catalytic systems of Cu
and only one catalytic system of
16
18
II
each Fe and In were employed for the coupling between
boronic acids and diphenyldiselenide. But most of the reactions
used toxic or expensive ligands, hazardous solvents, microwave
irradiation etc. which are not desired in the context of green
chemistry.
II
Herein, we have developed a simple and green method for
the synthesis of a series of organoselenides via C–Se bond
forming cross-coupling reaction between aryl boronic acids and
diphenyldiselenide catalyzed by Cu-loaded nitrogen rich CIN-1
II
(
Cu -CIN-1) in PEG-600 solvent (Scheme 1).
Result and discussion
Synthesis and characterization of CIN-1
The covalent imine network (CIN-1) was synthesized by the
reaction of piperazinedicarboxaldehyde with melamine under
ꢀ
reuxing condition in DMSO at 180 C under N atmosphere.
2
Then it was characterized by TEM and EDX analyses.
II
Cu -CIN-1 was synthesized by immobilizing Cu(OAc)
2
onto
the surface of CIN-1 material. Cu(OAc)
2
was added to a stirred
suspension of CIN-1 in dry acetone at room temperature and
then the stirring was continued for 48 h. The solid residue was
then ltered and washed with acetone followed by drying at
ꢀ
II
8
0 C to afford the Cu -CIN-1 catalyst. It was then characterized
by the following analyses.
X-ray diffraction
II
Small angle powder XRD pattern of the sample Cu -CIN-1 is
ꢀ
shown in Fig. 1. A broad peak is obtained at 2q ¼ 20–25 due to
amorphous nature of imine network. This result agrees well
with the small angle powder XRD pattern of the parent CIN-1
10
material. Some distinct sharp peaks observed at 2q values
II
with 10.28, 12.65, 25.1 degrees for Cu -CIN-1 could be assigned
due to presence of crystalline features originated due to the
II
binding of Cu(OAc)
2
at the pore surface.
Fig. 2 TEM images of (a) CIN-1 and (b) Cu -CIN-1 material.
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in the Fig. 3. Presence of C, N and Cu in the material is evident
from this prole. It is to be noted that Cu is present in the
specimen grid used for TEM analysis. But EPR and XPS analysis
II
conrm the presence of Cu in the Cu -CIN-1 material as Cu(II)
oxidation state (see below).
Thermal analysis
The quantitative determination of the organic content and the
II
framework stability of the Cu -CIN-1 sample are obtained from
2
the thermogravimetric analysis (TGA) under N ow. TGA curve of
II
Cu -CIN-1material is shown in Fig. 4. The TGA of this material
ꢀ
showed the rst weight loss below 100 C due to desorption of
absorbed water. This was followed by a gradual decrease in the
ꢀ
weight aer 380 C.Thus this thermal analysis data suggested that
II
Fig. 5 EPR spectrum of fresh Cu -CIN catalyst.
II
ꢀ
Cu -CIN-1 sample is stable up to 380 C (Fig. 4).
Electron paramagnetic resonance spectroscopy
To know the oxidation state of copper in the catalyst, we have
carried out the EPR (Electron Paramagnetic Resonance)
II
Fig. 6 The XPS data of Cu -CIN-1 material.
II
Fig. 3 EDAX analysis of the Cu -CIN-1 material.
II
II
Fig. 4 The TGA plot of the Cu -CIN-1 material.
Fig. 7
N
2
sorption analysis of CIN-1(a) and Cu -CIN-1(b).
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19
literature values. There is also a satellite peak present in the
XPS spectrum, which is a feature of 2p / 3d satellite peak of Cu
2
+
in +2 oxidation state. For pure and uniform Cu ions, the
intensity ratio of the satellite to the 2p3/2 peak is ordinarily 0.5.
II
For our Cu -CIN-1 sample the ratio is 0.51 which further reveals
that pure Cu(II) specie is present in the sample. Based on the
II
XPS results, the Cu species in the Cu -CIN-1 is found to be in
the +2 oxidation state.
N adsorption–desorption
2
N sorption analysis revealed the porous nature of CIN-1 and
2
II
Cu -CIN-1 materials (Fig. 7). Calculated BET surface area of
II
2
ꢁ1
CIN-1 and Cu -CIN-1 materials are 605 and 550 m
g
respectively. Pore size distribution plots obtained by using
NLDFT model suggested the peak pore widths of 1.37 and 1.12
II
II
Fig. 8 The DRS-UV-visible absorption spectrum of CIN-1 (a) and Cu - nm, respectively for CIN-1 and Cu -CIN-1. Respective pore
3
ꢁ1
3
ꢁ1
CIN-1 material.
volumes are 0.21 cm g and 0.19 cm g . The decrease in
surface area, pore size as well as pore volume reect the
successful loading of bivalent Cu(II) over CIN-1 material.
spectroscopic analysis for the fresh catalyst for the solid state at
room temperature (Fig. 5). The four hyperne lines of the cor-
responding spectrum were obtained due to the coupling of the
unpaired electron of copper with its nucleus which indicates the
presence of copper in its +2 oxidation state in Cu -CIN-1
catalyst.
FT-IR spectroscopy
II
FT-IR spectrum of Cu -CIN-1 shows stretching frequencies for
imine (C]N) at 1630, 1193 cm . The distinct bands related to
quadrant (1551 cm ) and semicircle stretching (1477 cm
ꢁ
1
II
ꢁ
1
ꢁ1
)
indicates presence of the triazine ring in the spectrum of CIN-1
9
material. Details assignments of FT-IR peaks are given in ESI
(Fig. S1†).
X-ray photoelectron spectroscopy (XPS)
II
The XPS spectrum of the Cu -CIN-1 catalyst is shown in Fig. 6.
The binding energy values 935.6 and 955.8 eV corresponding to
UV-vis DRS analysis
II
the spin orbit splitting components of Cu 2p3/2 and Cu 2p1/2 in The UV-vis absorption spectrum of the CIN-1 and Cu -CIN-1
the +2 oxidation state of copper agrees well with the reported catalyst were recorded in diffuse reectance mode as a BaSO
4
a
Table 1 Optimization of reaction conditions
ꢀ
b
Entry
Base
Solvent
Temp ( c)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
Cs
Cs
Cs
Cs
Cs
Cs
2
2
2
2
2
2
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
DMF
DMSO
PEG-600
H O
2
Toluene
THF
PEG-600
PEG-600
PEG-600
PEG-600
PEG-600
PEG-600
PEG-600
120
120
120
80
110
60
120
100
80
70
80
80
80
10
10
10
10
10
10
10
10
10
10
8
76
78
88
—
—
—
88
88
88
78
88
71
67
K
2
K
2
K
2
K
2
K
2
K
2
K
2
CO
CO
CO
CO
CO
CO
CO
3
3
3
3
3
3
3
1
1
1
1
0
1
2
3
6
8
c
a
II
2 3
Reaction conditions: 4-methoxy phenylboronic acid (1 mmol),diphenyldiselenide (0.5 mmol), K CO (1.5 mmol), Cu -CIN (0.1 mol% of Cu), PEG-
00 (5 ml). Yields refer to those of isolater pure products. 0.05 mol% of Cu was used.
b
c
6
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disk due to its solubility limitations in common organic nm is due to the p–p* transition of the conjugated system
II
solvents. The UV spectra of the extracted CIN-1 (a) and Cu -CIN- present in the covalent imine network. In the case of the Cu-
1
(b) are given in Fig. 8. In both case peaks in between 200–350 loaded sample a small hump at around 305–340 nm is
II
a
Table 2 Cu -CIN-1 catalyzed cross-coupling between aryl boronics and diphenyl diselenide
b
Entry
1
R
Product
Time (h)
8
Yield (%)
Ref.
17g
88
82
2
3
4
9
9
17n
17a
83
80
10
17m
5
6
7
9
9
88
84
85
18b
17g
17g
10
8
9
10
8
79
88
17g
17g
1
0
10
85
17b
1
1
1
2
10
10
79
85
17m
—
a
b
II
Reaction conditions: boronic acid (1 mmol), diphenyl diselenide (0.5 mmol), K
Yields refer to those of isolater pure products.
2
CO
3
(1.5 mmol), Cu -CIN (0.1 mol% of Cu), PEG-600(5 ml).
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present can be attributed due to LMCT. In addition to this, a 2-methoxypyridine-5-boronic acid upon phenyl selenylation
broad absorption band in between 600–800 nm is observed. produced heteroaryl-aryl selenide (Table 2, entry 12).
+
2
20
This could be attributed to the d–d transition of Cu ion.
To know the oxidation state of copper aer the reaction in
Cu -CIN-1, we have performed EPR (Electron Paramagnetic
II
Resonance) spectroscopic analysis of the used catalyst in its
solid state at room temperature (Fig. 9), which also showed
similar type of spectrum with the fresh catalyst (Fig. 5). Hence,
it is evident that the oxidation state of copper remains
unchanged aer the reaction.
Catalytic activity
To optimise the reaction conditions, a series of experiments
were carried out with the variation of base, solvent, temperature
and time for a representative reaction between 4-methoxy
phenyl boronic acid and diphenyldiselenide in presence of 0.1
II
mol% of Cu in Cu -CIN-1. The results are summarized in Recycling of catalyst
Table 1. Among various solvents like DMF, DMSO, PEG-600,
For a heterogeneous catalyst, it is important to examine its ease
of separation from the reaction mixture, recoverability and
reusability. The reusability of the Cu -CIN-1 catalyst was
investigated for the representative C–Se cross coupling reaction
between 4-methoxy phenylboronic acid and diphenyldiselenide
H
(
2
O, toluene and THF, PEG-600 was found to be the best
Table 1, entries 1–7). Both the carbonate base, i.e. Cs CO and
showed equal activity for the selenylation reaction. But
being cheaper and milder than Cs CO , it was consid-
2
3
II
K
K
2
2
CO
CO
3
3
2
3
ered as the choice of base. The best result in terms of yield and
time was obtained by carrying out the reaction in PEG-600, in
(Table 2, entry 9). Aer the rst cycle of the reaction, catalyst was
ꢀ
recovered by simple ltration through a sintered glass-bed (G-4)
presence of K CO at 80 C for 8 h (Table 1, entry 11). It was also
2
3
and washed with ethanol followed by acetone which was then
observed that with the decrease of catalyst loading from 0.1
mol% of copper, yield of product also decreases (Table 1,
entry 13).
Several diversely substituted aryl boronic acids were sub-
jected for the selenylation reaction using diphenyldiselenide to
synthesize a library of organoselenides under the standardised
reaction conditions. The results are tabulated in Table 2. Both
electron-donating and electron-withdrawing group substituted
ꢀ
dried in an oven at 100 C. The performance of the recy-
cledcatalyst for the representative reaction was tested with time
(h) upto six successive runs and the corresponding kinetic plots
are shown in Fig. 10. These plots clearly suggest that the cata-
lytic efficacy of the recovered catalyst remained almost the same
aer six reaction cycles.
aryl boronic acids underwent phenyl selenylation reaction Heterogeneity test
smoothly. Various electron withdrawing substituents like CHO,
To examine whether copper was being leached out from the
solid support to the solution, a typical test was performed in
C–Se cross coupling reaction between 4-methoxy phenyl-
boronicacid and diphenyldiselenide (Table 2, entry 9) with our
supported Cu -CIN-1 catalyst. For the various proof of hetero-
geneity, a test was carried out by ltering catalyst from the
reaction mixture aer 6 h and the ltrate was allowed to react
CO
Base-sensitive functionalities (CO
intact under the mild basic reaction conditions (Table 2, entries
and 5). Halide containing aryl boronic acid, i.e. 4-bromo-
2
Et, CN, CF
3
and NO
2
were compatible (Table 2, entries 2–7).
2
Et, CN) were remained
4
II
phenyl boronic acid produced halide containing organo-
selenide (Table 2, entry 8). Electron donating group i.e., OMe
containing aryl boronic acids were also reacted with diphenyl-
diselenide without any difficulties (Table 2, entry 9, 10 and 12).
Two napthyl boronic acids produced two analogous of 5-LOX
11e
(
Lipoxygenase) inhibitor aer phenyl selenylation (Table 2,
entries 10 and 11). Heteroaryl substituted boronic acid i.e.
II
Fig. 10 Kinetic plot of recycling test of catalyst (Cu -CIN-1) in the
C–Se cross coupling reaction between 4-methoxy phenylboronic acid
and diphenyldiselenide.
II
Fig. 9 EPR spectrum of used Cu -CIN-1 catalyst.
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up to the completion of the reaction (8 h). In this case no change analysis (TGA) was carried out using a Mettler Toledo TGA/DTA
in conversion was observed, which suggests that the catalyst is 851e. The EPR (electron paramagnetic resonance) spectra were
heterogeneous in nature. No evidence for leaching of copper or recorded for the solid sample at room temperature using a JES-
1
decomposition of the complex catalyst was observed during the FA200ESR spectrometer (JEOL). H NMR spectra were recorded
catalytic reaction. It was noticed that aer ltration of the on a Bruker 300 MHz, 400 MHz and 500 MHz spectrometers.
catalyst from the reaction mixture, reaction do not proceed
further. Atomic absorption spectrometric analysis of the
supernatant solution of the reaction mixture thus collected by
Preparation of the catalyst

ltration also conrmed the absence of copper ions (below
Synthesis of covalent imine network material CIN-1. Pipar-
detection limit of AAS) in the liquid phase. Thus, results of the azinedicarbaldehyde (169 mg, 1.19 mmol) and melamine (100
above test suggested that Cu was not being leached out from the mg, 0.79 mmol) were stirred with dimethyl sulfoxide (12 ml) in a
solid catalyst during the reactions.
round bottom ask tted with a reux condenser, at 453 K for
2 h in dry N atmosphere. Aer cooling to room temperature,
7
2
the white precipitate was ltered over a Buchner funnel and
washed using dry ethanol, excess dry acetone, THF and
dichloromethane sequentially. Finally the white solid product
Conclusions
In conclusion, we have developed an easy and green procedure
for the phenylselenylation of arylboronic acids catalysed by a
newly synthesized heterogeneous Cu(II) catalyst supported on
was dried under vacuum to obtain solvent free powder (257 mg,
9
9
5.5% yield) CIN-1material.
II
II
Synthesis of the Cu -CIN-1 catalyst. CIN-1 (250 mg) and
nitrogen rich porous covalent imine network (Cu -CIN-1) in
copper acetate (15 mg) were added to dry acetone (20 ml). Then
it was stirred at room temperature (298–300 K) for 48 h. When
light green coloured solid appeared, it was then ltered through
G-4 sintered glass crucible and washed with acetone (4 ꢂ 5 mL)
PEG-600 solvent. The catalyst provides few advantages for the
selenylation reaction, like ligand-free protocol, mild reaction
conditions, efficient phenylselenylation using very low copper
content (0.1 mol%), high TOF of the catalyst, reaction at PEG-
2
to remove any trace amount of unreacted Cu(OAc) . Then it was
600 which is a green solvent, general applicability, high yields
dried in the oven at 353 K for overnight to provide an easy
owing light green powder. This CIN-1 supported Cu catalyst
Cu -CIN-1 (Cu content ¼ 0.42 wt%, determined by AAS) was
used for all the C–Se cross coupling reactions.
of products and recyclability of the catalyst for six runs without
any appreciable loss of activity. To the best of our knowledge, we
are not aware of such green selenylation of aryl boronic acids
using an efficient and highly recyclable copper catalyst and this
will make an important addition to the existing procedures.

II
Experimental for carbon–selenium cross coupling reaction of
Experimental section
Materials
4-methoxy phenylboronic acid with diphenyldiselenide
catalyzed by Cu -CIN-1 catalyst (Table 2, entry 9)
II
To a solution of 4-methoxy phenylboronic acid (152 mg, 1
Melamine, 1,4-piparazine dicarbaldehyde and all boronic acids
were purchased from Sigma-Aldrich. Diphenyldiselenide was
purchased from Merck, Germany. Copper acetate (Cu(OAc)2),
potassium carbonate (K CO ) were purchased from Merck,
India. All other reagents and solvents were purchased from
commercial sources and were used without further purication.
Solvents were dried and distilled through standard procedure.
mmol) and diphenyldiselenide (156 mg, 0.5 mmol) in 10 ml
II
PEG-600, K
2
CO
3
(207 mg, 1.5 mmol) and Cu -CIN-1 catalyst (20
ꢀ
mg, 0.1 mol%) were added. The mixture was stirred at 80 C for
2
3
8
h. The progress of the reactions was monitored by TLC. Aer
the reaction the catalyst was ltered through a sintered glass
bed (G-4) and washed with water followed by acetone and dried
in oven. The ltrate was extracted three times with ethyl acetate
(
3 ꢂ 20 ml) and washed with water. The organic layers were
Physical measurements
combined and dried with anhydrous Na SO . Then the solvent
2
4
Powder X-ray diffraction (XRD) patterns of different samples was evaporated to dryness under vacuum. The residue was then
were analyzed with a Bruker D8 Advance X-ray diffractometer puried by column chromatography on silica gel to provide the
using Ni-ltered Cu Ka (l ¼ 0.15406 nm) radiation. Trans- desired product as a pale yellow liquid (134 mg, yield 88%); TOF
ꢁ
1
ꢁ1 1
mission electron microscopic (TEM) images of the porous ¼ 110 h ; IR (neat) 3065, 2922, 2831, 1576, 1470, 1280 cm ; H
polymer were obtained using a JEOL JEM 2010 transmission NMR (500 MHz, CDCl
electron microscope operating at 200 kV. The copper content of 7.18–7.21 (m, 3H), 7.32 (d, J ¼ 7 Hz, 2 Hz); C NMR (125 MHz,
the samples was measured by Varian AA240 atomic absorption CDCl ) d 55.4, 115.3 (2C), 120.2, 126.6, 129.4 (2C), 131.1 (2C),
spectrophotometer (AAS). Nitrogen adsorption/desorption 133.4 (2C), 136.6 (2C), 159.8. These spectroscopic data (IR, H
isotherms of were obtained by using a Quantachrome Auto- NMR, and C NMR) are in good agreement with those of the
sorb 1C surface area analyzer at 77 K. Prior to gas adsorption, authentic compounds reported earlier. This procedure was
samples were degassed for 4 h at 393 K under high vacuum. UV- followed for all the reactions in Table 2. Most of these products
visible diffuse reectance spectra were recorded on a Shimadzu are known in literature and these are identied by a comparison
UV 2401 PC coupled with an integrating sphere attachment. of their spectroscopic data with those previously reported (see
3
) d 3.82 (s, 3H), 6.86 (d, J ¼ 7 Hz, 2H),
13
3
1
1
3
4
BaSO was used as background standard. Thermogravimetric references in Table 2). The product which is not reported earlier
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1
13
was characterized by its H NMR and C NMR spectroscopic
data and elemental analysis, which is provided below.
7 (a) L. Wang, A. Reis, A. Seifert, T. Philippi, S. Ernst, M. Jia and
W. R. Thiel, Dalton Trans., 2009, 3315–3320; (b) S. K. Das,
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2
-Methoxy-5-phenylselanyl-pyridine (Table 2, entry 12). Light
yellow liquid (85%); IR (neat) 3025, 2927, 1731, 1563, 1463,
412, 1379, 1187, 1032 cm ; H NMR (400 MHz, CDCl ) d 3.94
3
ꢁ
1 1
1
(
2
s, 3H), 6.70 (d, J ¼ 7 Hz, 1H), 7.20–7.24 (m, 3H), 7.34–7.36 (m,
1
3
H), 7.73 (dd, J
) d 53.7, 112.2, 118.0, 127.0, 129.4 (2C), 131.4 (2C),
32.1, 145.3, 152.4, 164.1. Anal. calcd for C12 11NOSe: C, 54.56;
1
¼ 8.4, J ¼ 5.2, 1H), 8.37 (s, 1H); C NMR (100
2
MHz, CDCl
3
1
H
H, 4.20; N, 5.30%. Found: C, 54.50; H, 4.24; N, 5.33%.
8
9
H. Yoon, S. Ko and J. Jang, Chem. Commun., 2007, 1468.
(a) C. E. Chan-Thaw, A. Villa, P. Katekomol, D. Su, A. Thomas
and L. Prati, Nano Lett., 2010, 10, 537–541; (b) D. Damodara,
R. Arundhathi and P. R. Likhar, Catal. Sci. Technol., 2013, 3,
797–802.
Acknowledgements
SMI acknowledges the Council of Scientic and Industrial
Research (CSIR) and Department of Science and Technology
(DST), New Delhi, India for funding. We acknowledge DST for 10 M. K. Bhunia, S. K. Das, P. Pachfule, R. Banerjee and
providing support to the University of Kalyani under Purse and
A. Bhaumik, Dalton Trans., 2012, 41, 1304–1311.
FIST programme. BB acknowledges Council of Scientic and 11 (a) G. Mugesh, W. W. du Mont and H. Sies, Chem. Rev., 2001,
Industrial Research (CSIR) for SPM fellowship. AB wishes to
thank DST-SERB, New Delhi for extramural project grant and
DST Unit on Nanoscience for providing instrumental facilities
at IACS.
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