CuIBiOI is an efficient novel catalyst in Ullmann-type CN– couplings with wide scope—A rare non-photocatalyic application

Article abstract of DOI:10.1016/j.mcat.2020.111072

Preparation of a new, mixed-cationic layered Cu^IBiOI was prepared and its non-photocatalytic catalytic properties were explored. This solid substance had BiOI-like, lamellar and deflected structure resulting from Cu^I ion incorporation in the Bi₂O₂ layers. The as-prepared substance was fully characterized by XRD, Raman, far IR, UV–DR, XP spectroscopies, thermal (TG-DTG) and analytical (ICP-MS, SEM-EDX) methods, electron microscopies (SEM, TEM) as well as BET surface area measurements. By performing Ullmann-type CN– coupling reactions between aryl halides and aqueous ammonia, its catalytic capabilities were tested. The effects of solvents, added base and catalyst loading as well as reaction time and reaction temperature were scrutinized, and a green way for the reaction was identified. The recyclability of the catalyst without the loss of activity and its general applicability for a wide range of aryl halides were also demonstrated.

Full text of DOI:10.1016/j.mcat.2020.111072

MolecularCatalysis493(2020)111072
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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat
CuIBiOI is an efficient novel catalyst in Ullmann-type CNe couplings with
wide scope—A rare non-photocatalyic application
Gábor Vargaa,b,*, Marianna Kocsisa,b, Ákos Kukoveczc, Zoltán Kónyac,d, Igor Djerdje, Pál Siposb,f,
István Pálinkóa,b,
*
a Department of Organic Chemistry, University of Szeged, Dóm Tér 8, Szeged, H-6720 Hungary
b Materials and Solution Structure Research Group, and Interdisciplinary Excellence Centre, Institute of Chemistry, University of Szeged, Aradi Vértanúk tere 1, Szeged, H-
6720, Hungary
c Department of Applied and Environmental Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged, H-6720, Hungary
d MTA-SZTE Reaction Kinetics and Surface Chemistry Research Group, Rerrich Béla tér 1, Szeged, H-6720, Hungary
e Department of Chemistry, J. J. Strossmayer University of Osijek, Cara Hadrijana 8/a, Osijek, HR-31000, Croatia
f Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, Szeged, H-6720, Hungary
A R T I C L E I N F O
A B S T R A C T
Keywords:
Preparation of a new, mixed-cationic layered CuIBiOI was prepared and its non-photocatalytic catalytic prop-
erties were explored. This solid substance had BiOI-like, lamellar and deflected structure resulting from CuI ion
incorporation in the Bi2O2 layers. The as-prepared substance was fully characterized by XRD, Raman, far IR,
UVeDR, XP spectroscopies, thermal (TG-DTG) and analytical (ICP-MS, SEM-EDX) methods, electron micro-
scopies (SEM, TEM) as well as BET surface area measurements. By performing Ullmann-type CNe coupling
reactions between aryl halides and aqueous ammonia, its catalytic capabilities were tested. The effects of sol-
vents, added base and catalyst loading as well as reaction time and reaction temperature were scrutinized, and a
green way for the reaction was identified. The recyclability of the catalyst without the loss of activity and its
general applicability for a wide range of aryl halides were also demonstrated.
Synthesis of CuIBiOI
Structural characterization
Spectroscopies (far IR, Raman, UV-DR, XP, ICP-
MS)
Electron microscopies (SEM, TEM)
Thermal methods
eUllmann-type CN coupling reactions
1. Introduction
For instance, bismuth oxohalides only gained attention, it was re-
markable though, as photocatalysts [40]. Bismuth oxohalides with a
Since the low-cost, easy availability and low-toxicity of bismuth and
its compounds [1] qualify it as green element [2], bismuth compounds
have been utilized as efficient low-cost environmentally benign Lewis
acidic catalysts in a wide variety of synthetic organic transformations
[3–5]. Many attempts were performed to design homogeneous bismuth
catalysts for Strecker synthesis [6,7], Biginelli [8–12], Pictet–Spengler
[13,14], aldol [15,16] and Michael reactions [17,18], Friedel-Crafts
acylation [19–22], rearrangements (Fries, Beckmann, Ferrier) [23–26]
as well as aromatization (Hantzsch) reactions [27]. However, few ex-
amples can only be found in the literature concerning the application of
heterogeneous or heterogenized bismuth-containing systems in non-
photocatalytic applications [28,29].
The main uses of bismuth-containing materials, the non-lamellar
oxides [30], perovskites [31], lamellar double salts [32], oxohalides
[33], perovskites [34] and superstructures [35,36] such as Sillen-Aur-
ivillius [37] structures are in the field of photochemistry [38] or pho-
tovoltaic science [39].
tetragonal matlockite structure (space group P4/nmm) precipitated in
lamellar structures consisting of [X–Bi–O–Bi–X] bonded layers are kept
together with non-covalent interactions through the halogen···halogen
close contacts along the c axis [41]. Generally, the photocatalytic
capabilities of the BiOX systems could be enhanced by systematically
varying the particle size of the materials [42], the surface-to-volume
ratios [43], exchanging the counter ions [44] or modifying the porosity
[45]. There are some studies, which concern doping of the parent BiOX
materials with metal ions. CaII [46], SrII [47], PbII [48], MnII [49], FeIII
[50], CoII [51] and CuII [52–54] were used for this purpose, and they
usually enhanced the photocatalytic activities of the parent substance.
For instance, CuII doping meant deposition of CuII salt onto the surface
of BiOCl, and visible light photoactivity was observed [52].
In this contribution, the insertion of CuI ions, proven by a range of
instrumental methods, is described into the structure of BiOI for the
first time. The material obtained was tested as catalyst in a non-pho-
tocatalytic reaction, in an Ullmann-type reaction. It is the CNe coupling
⁎ Corresponding authors at: Department of Organic Chemistry, University of Szeged, Dóm Tér 8, Szeged, H-6720 Hungary.
E-mail addresses: gabor.varga5@chem.u-szeged.hu (G. Varga), palinko@chem.u-szeged.hu (I. Pálinkó).
https://doi.org/10.1016/j.mcat.2020.111072
Received 24 April 2020; Received in revised form 28 May 2020; Accepted 6 June 2020
2468-8231/©2020TheAuthor(s).PublishedbyElsevierB.V.ThisisanopenaccessarticleundertheCCBY-NC-NDlicense
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).

G. Varga, et al.
MolecularCatalysis493(2020)111072
reaction catalyzed by copper species, known for a long time [55], but
intensively researched and applied in recent times as well [56–60]. This
method has now acquired great significance considering its potential in
environmentally benign uses in drug-related syntheses [61]. It is to be
noted that, by applying organic additives, numerous methods for
copper-mediated reactions under homogeneous conditions have been
developed [62]. On the contrary, the studies focusing at reusable cat-
alysts only form a small fraction of the published articles. In these
works, various types of supports were applied for anchoring copper
species of different oxidation states to perform condensation of un-
saturated N heterocycles with aryl halides [63–65]. Furthermore, the
catalytic performance of self-supported catalysts were only described in
one paper, the application of Cu2O-coated Cu(0) or nano-Cu(0) pro-
vided with acceptable yield [66]. Until now, Cu(I) inserted USY (zeo-
lite) seemed to be the most efficient heterogeneous Cu-containing
system [67].
operating at an acceleration voltage of 200 kV.
The Raman spectra were recorded with a Thermo Scientific TM
DXRTM Raman microscope at an excitation wavelength of 635 nm
applying 10 mW laser power and averaging 20 spectra with an ex-
position time of 6 s. UV–DR spectra were registered on an Ocean Optics
USB4000 spectrometer with a DH-2000-BAL UV–Vis–NIR light source
measuring diffuse reflectance using BaSO4 as reference. The spectra
were analyzed with the SpectraSuite package. For the identification of
MOe/I vibrations, the far IR spectra were recorded with a BIO-RAD
Digilab Division FTS-40 vacuum FT–IR spectrophotometer (4 cm−1
resolution, 256 scans). The Nujol mull technique was used between two
polyethylene windows (the suspension of 10 mg sample and a drop of
Nujol mull).
X-ray photoelectron spectra (XPS) were recorded using a SPECS
instrument equipped with a PHOIBOS 150 MCD 9 hemispherical elec-
tron energy analyzer using Al Kα radiation (hν =1486.6 eV). The X-ray
gun was operated at 210 W (14 kV, 15 mA). The analyzer was operated
in the FAT mode, with the pass energy set to 20 eV. The step size was 25
meV, and the collection time in one channel was 250 ms. Typically,
5–10 scans were added to acquire a single spectrum. Energy referencing
was not applied. In all cases the powder-like samples were evenly laid
out on one side of a double-sided adhesive tape, the other side being
attached to the sample holder of the XPS instrument. The samples were
evacuated at room temperature, and then inserted into the analysis
chamber of the XPS instrument.
BET surface area measurements were performed on a NOVA3000
(Quantachrome) instrument. The samples were degassed with N2 at 100
°C for 5 h under vacuum to clean the surface of adsorbed materials. The
measurements were performed at the temperature of liquid N2.
The thermal behavior of the samples were investigated by thermo-
gravimetry (TG) and differential thermogravimetry (DTG). The samples
were studied in a Setaram Labsys derivatograph operating in air at 5 °C
min−1 heating rate. For the measurements, 20–30 mg of the samples
were applied.
The actual ratios of metal ions in the oxohalides were determined by
Agilent 7700× Inductively Coupled Plasma Mass Spectrometer
(ICP–MS). Multielemental internal standard was used for each mea-
surement. Before measurements, few milligrams of the samples mea-
sured by analytical accuracy were dissolved in 5 ml of cc. HNO3. After
dissolution, the samples were diluted with distilled water to 100 ml and
filtered.
The results obtained and their interpretation are communicated in
the followings.
2. Experimental
2.1. Materials, synthetic and pretreatment procedures
All the chemicals (Bi(NO3)3×5 H2O, CuI, cc. HNO3, KI, aryl halides
(iodobenzene; chlorobenzene; bromobenzene; 2-chlorophenol; 3-
chlorophenol; 1-chloronaphtalene, 1,2-dichlorobenzene; 1,3-dicglor-
obenzene; 1-chloro-2-nitrobenzene; 1-chloro-3-ntirobenzene; 2-chlor-
opyridine; 4-chloroquinoline and 10-chloro-9-anthraldehyde), 25 %
NH3 aqueous solution, applied bases (K2CO3, K3PO4, Cs2CO3, pyridine,
piperidine), OH–L-proline, Na2SO4, hexane, ethyl acetate, diethyl ether,
applied solvents (dimethyl sulfoxide (DMSO), acetone, toluene, tetra-
hydrofuran (THF), 96 % ethanol) were purchased from Sigma-Aldrich
in analytical purity and were used as received. Purified water was
produced by reverse osmosis and UV irradiation processes by a Puranity
TU 3 + UV/UF system (VWR).
The catalysts were prepared by a modified co-precipitation method.
Aqueous solution of KI (V =25 mL; c = 0.12 M) and varying amounts
of CuI (n = 5.25 × 10–4 – 2.1 × 10–3 mol) were made and treated by
15-minute-long ultrasonic irradiation. In another flask, Bi(NO3)3×5
H2O (n = 1.2 × 10–3 mol) was dissolved in 25 ml of 5 % HNO3. This
solution was prepared with 60-minute-long ultrasonic irradiation.
Then, under continuous stirring, the BiIII-containing solution was added
dropwise to the CuI-containing solution. The mixture was stirred at
room temperature for 60 min, then at 90 °C for 168 h. The materials
obtained were separated by centrifugation (1800 rpm) followed by
filtration, washed with hot (∼60 °C) distilled water and ethanol several
times, and dried at 60 °C for 24 h. BiOI, for comparison, was made in
the same way, but without CuI.
2.3. Catalytic procedure for the Ullmann-type CNe coupling reactions
For testing the catalytic capabilities of oxohalides, Ullmann-type
CNe coupling reactions were carried out. The mixtures of CuI (0.01–0.1
mmol) or CuIBiOI (0.01–0.1 mmol for Cu) or BiOI (0.01–0.1 mmol for
Bi) catalyst, organic additive (0.05 mmol, OH–L-proline only for CuI),
(hetero)aryl halide (0.5 mmol), base (1.0 mmol) and aqueous ammonia
(1.0 mmol) as well as 3.0 ml of solvent were stirred in a 10 ml flask in
N2 atmosphere for 1–24 h, at 25–110 °C. After cooling to room tem-
perature, the crude product was diluted with ethyl acetate (∼40 ml).
The organic phase was separated and the aqueous phase was extracted
with ethyl acetate twice. The combined organic phase was dried over
Na2SO4. The product was purified by silica gel chromatography using
solvent mixtures (ethyl acetate/hexanes, diethyl ether/hexanes).
At the end of the reactions, the mixtures were analyzed on a
Hewlett-Packard 5890 Series II gas chromatograph equipped with flame
ionization detector using an Agilent HP-1 column and the internal
standard technique using toluene. The temperature was increased in
stages from 50 °C to 300 °C. The products were identified via using
authentic samples.
Cu0.48Bi2.52O4 was obtained by heat treatment of the CuIBiOI ma-
terial at 550 °C for 2 h. α-Bi2O3 was produced by heat treatment of BiOI
catalyst at 750 °C for 2 h.
2.2. Methods of structural characterization
X-ray diffraction (XRD) patterns were recorded on a Rigaku XRD-
MiniFlex II instrument applying Cu Kα radiation (λ =0.15418 nm)
with 40 kV accelerating voltage at 30 mA.
The morphology of the freshly prepared samples was studied by
scanning electron microscopy (SEM). The SEM images were registered
on an S-4700 scanning electron microscope (SEM, Hitachi, Japan) with
accelerating voltage of 10–18 kV. EDX data were obtained with a
Röntec QX2 energy dispersive microanalytical system from two dif-
ferent parts of the sample. The coupled system also provided with the
elemental map. More detailed images of the as-prepared samples were
produced by transmission electron microscopy (TEM). For these mea-
surements, a FEI Tecnai™ G2 20 X-Twin type instrument was used
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G. Varga, et al.
MolecularCatalysis493(2020)111072
Fig. 1. XRD patterns of Cu@BiOI heterostructures with various amounts of added CuI. A: 5.25 × 10–4 mol CuI; B: 1.05 × 10–3 mol CuI; C: 2.10 × 10–3 mol CuI.
3. Results and discussion
The Raman spectrum of material produced is seen in Fig. 2, trace B.
It displays four Raman bands at 87, 112, 148 and 358 cm–1. The bands
at 87 and 148 cm–1 are associated with the A1g mode of the (Bi–X)
stretching vibrations of the iodine centers around the tetragonal [001]h
direction [74] and Eg mode of the pure Bi(–X) vibration in the tetra-
gonal [001]h plane. These are halogen-sensitive bands [75]. These
peaks are centered at exactly the same position as for BiOI indicating
that the Bi–X units are the same [76]. The two bands at around 112 and
358 cm–1 are the shifted A1g mode of translational vibration of the CuO4
plane along the Z-axis [77] and the shifted Bg mode related to the
oxygen atom vibrations in the Cu–O–M lattice [78]. These observations
verify that all of the Raman and IR vibrations bands related to Bi–O or
Cu–O units are shifted confirming again that CuI insertion occurred,
indeed.
3.1. Structural analysis of the CuIBiOI material
Fig. 1 displays the XRD patterns of CuIBiOI prepared by modified co-
precipitation with various amounts of CuI. The diffractograms confirm
the formation of well-crystallized solid samples with tetragonal unit cell
of P4/nmm space group, an analogous structure to layered bismuth
oxoiodide (JCPDS File No. 73-2062) [68]. However, the intensities of
several peaks changed significantly (the Miller indices of the relevant
peaks are written in bold) indicating possible CuI insertion. It is to be
noted that the ratio of CuI (JCPDS # 83-1137) side-product increased
with increasing CuI dosage. Phase purity was achieved by using 1:6
nominal molar ratio of CuI and BiIII cations (Fig. 1, trace A). On the
basis of ICP-MS and SEM-EDX measurements, the actual composition
To investigate the oxidation states of the cationic components of the
CuIBiOI material, X-ray photoelectron spectroscopy analysis was car-
ried out, and the results are displayed in Fig. 2/C and D. Fig. 2/C
presents the 4f region of bismuth, which includes two well-resolved
peaks at around 159.65 and 165.90 eV. The binding energies corre-
spond to Bi 4f7/2 and Bi 4f5/2, respectively, demonstrating that the main
oxidation state of Bi in the samples was +3 [79]. Fig. 2/D shows the
core level of the Cu 2p spectra. The location of the deconvoluted main
peak related to the Cu 2p3/2 transition indicates the presence of Cu° or
CuI species in the structure [80]. The absence of the shake-up lines
(satellite peaks) attest that the main peak can be attributed to CuI va-
lance state [81]. Cu 2p peak overlaps with two iodine peaks; the 930.20
eV binding energy is identified as I 3p1/2 transition [82]. The other,
broadened peak at about 926.10 eV due to Jahn-Teller effect, caused
distortion in the layered structure resulting in lower binding energies
(926.10 eV) for neighboring iodines [83]. The 3p transitions of iodine
are very sensitive to distortions contrary to the 3d peaks. The peak
located at ∼620 eV (Fig. S2) belongs to the 3d transition of iodine
species confirming its presence in chemical bond [84]. The peak at
∼533 eV is the oxygen [85]. All these results indicate the formation of
a deflected lamellar CuIBiOI structure as well.
was found to be Cu0.18Bi0.88O0.88 1.06 for the phase-pure product. On
I
performing a 550 °C heat treatment on the phase-pure product, a spinel
structure, analogous to CuIBi2O4, could be produced (Fig. S1, trace B –
“S” is used as prefix for the figures and the table in the Supplementary
Information file).
The lattice constants for the CuIBiOI product (a = b =3.989 Å; c
=9.416 Å) are very similar to those of the non-modified BiOI [69]. It
may be assumed that CuI ions replaced some of the BiIII ions in the
layers largely keeping original BiOI structure, but making it somewhat
deflected, since the CuI ion is smaller than the Bi(III) ion. Similar
phenomenon was observed when CuI ion was inserted into CeO2, which
also had tetragonal structure [70].
In order to collect further proofs for the insertion of CuI ions into the
[Bi2O2] units, the far IR and the Raman spectra were recorded. The far
IR spectrum of the phase-pure CuIBiOI sample is shown in Fig. 2, trace
A. This spectrum exhibits two characteristics bands at 450 and 618
cm–1. The strong absorption band observed at 450 cm–1 is related to the
stretching mode of the BiOe bonds of the BiO6 octahedron (ν(BiOe))
[71]. It is shifted to the lower energy compared to the previous pub-
lished wavenumber value of pure BiOI (489 cm–1). This shift of the
halogen insensitive band is attributed to the structural distortion of
[Bi2O2] units, in agreement with the experiences collected for modified
Sillén structures [72]. Comparing to other copper oxides, the small peak
at 648 cm–1 is identified as the shifted stretching vibration of the Cu–O
band in the assumed tetrahedral cell [73]. This shift can also be as-
signed to the insertion of the CuI ion into the lamellar structure.
In order to further verify CuI insertion, the optical behaviour of BiOI
and CuIBiOI were compared (Fig. 3/A and B). The diffuse reflectance
spectra (Fig. 3/A) of the BiOI and the CuIBiOI samples have similar
absorption profiles and maxima; however, due to CuI insertion [86], all
characteristic transitions underwent red shift. Since new bands did not
appear, thus, no new material was formed, this is an indication of CuI
3

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MolecularCatalysis493(2020)111072
Fig. 2. A: far IR, B: Raman, C: Bi 4f XP and D: deconvoluted Cu 2p XP spectra of the as-synthesized phase-pure Cu-containing BiOI analogue.
insertion into the BiOI structure. The calculated band gaps (Fig. 3/B)
also differ indicating structural modification.
Three main peaks appeared during calcination of CuIBiOI as well
(Fig. 3/D). The first weight loss around 160 °C may be attributed to the
phase transformation of CuIBiOI into a lower symmetry iodine-containg
phase. The second endothermic peak centered at about 299 °C may be
assigned to the collapse of the lamellar framework resulting in a mixed
CuBiO(I) structure [90]. The weight loss observed around 488 °C in-
dicates the formation of Cu0.48Bi2.42O4 spinel oxide, identified by X-ray
diffractometry (Fig. S1, trace B).
TG-DTA measurements were also carried out to investigate the
thermal behaviour of pure and Cu-modified BiOI. Three endothermic
peaks, centered at 215, 486 and 695 °C, appeared during the calcination
process of BiOI (Fig. 3/C). In the TG-DTA curve, the first peak (centered
at 215 °C) corresponds to BiOI to Bi4O5I2 transformation [87]. The
second main peak (centered at 486 °C) can be associated with the
transformation of Bi4O5I2 to Bi5O7I [88]. The third peak is related to
total calcination to form α-Bi2O3, which is identified by X-ray dif-
fractometry (Fig. S1, trace E – JCPDS # 41-1449) [89].
The as-prepared CuIBiOI particles are non-uniform in shape, and
consist of numerous nanoparticles as the TEM images attest (Fig. 4/
A–C). Small-sized nanoballs (C) build up the nanostructures with
Fig. 3. A: UV–DR spectra, B: (αhυ)1/2 vs. energy (hυ) plot for calculating the band gap energy and TG/DTG (C and D) curves for the as-prepared phase-pure C: BiOI
and D: the CuIBiOI.
4

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MolecularCatalysis493(2020)111072
Fig. 4. A–C: TEM images and D–E: SEM images of the CuIBiOI material.
thicknesses of 80–150 nm and lengths of approximately 200–800 nm.
SEM images (Fig. 4/D–E) reveal non-porous lamellar structure with
cauliflower morphology. The non-porous structure was confirmed by
BET measurement (Fig. S3) as well. The isotherm is of type IV isotherms
with H3 hysteresis loop, which describes lamellar structure without
hierarchically ordered pores [91]. Low specific surface areas (45–65
m2/g) were obtained for both the freshly prepared BiOI and CuIBiOI.
that as far as activity is concerned, CuIBiOI was competitive with the
homogeneous CuI−HO-L-proline containing system, in which HO–L-
proline was found to be the best performing organic additive [92]. It is
to be noted that the selectivity over both as-prepared composites and
with the homogeneous catalysts were 100 % for the amine product.
We hoped to further improve the performance of CuIBiOI by opti-
mizing the reaction conditions. Therefore, the effects of all relevant
parameters were explored, such as catalyst loading (Fig. S5; optimum: 4
%), type of base (Table S1; optimum: K3PO4), solvents and reaction
temperatures (Fig. S6) A moderately high temperature, 80 °C, at which
the original structure of CuIBiOI remained intact, and a green solvent
mixture, H2O/ethanol (Figs. S5, S6) were found to be optimal. CuIBiOI
catalyst is assumed to provide the most effective catalytic behavior
from the presented systems, because not only the Cu(I) centers but also
Bi(III) Lewis acidic centers take part in the catalytic process.
Accordingly, in this case, a bifunctional heterogeneous system is op-
erational. A possible reaction mechanism has been outlined in the
Supplementary Information document (Scheme S1).
3.2. Catalytic behavior of CuIBiOI
Copper-catalyzed coupling reaction of ammonia with aryl halides
have attracted much attention for a long time [56]. The organic ad-
ditive promoted Ullmann reactions gave major “push” to this field [57].
One of the most attractive homogeneous systems consists of CuI and
various organic promoters [58].
Our as-prepared CuIBiOI material and for comparison the BiOI
substance were tested in this reaction (Scheme 1) in the presence or
without organic additive and the homogeneous variant using CuI was
also probed (Fig. 5).
The recyclability of CuIBiOI catalyst was checked in six consecutive
runs under the optimal reaction conditions (Fig. 6). Slight deactivation
was only observed. Leaching did not occur by ICP-MS measurements,
and the lamellar structure was retained with some loss of crystallinity
as confirmed by X-ray diffractometry (Fig. S1, trace C). In order to
ensure the catalyst is indeed stable, the recycling measurements were
repeated with lower amount catalyst (0.02 mmol) removing the
To much of our surprise the reaction proceeded over BiOI using BiIII
ions as active centers. As it is expected the CuI-containing catalysts
(either homogeneous or heterogeneous) were significantly more active.
It is to be noted that over the heterogeneous catalyst there was no need
for organic additive, i.e. the reaction was greener than the one pro-
moted by the homogeneous catalyst. It is also important to point out
Scheme 1. Ullmann-type CNe coupling reaction between aryl
halides and aqueous ammonia catalyzed by oxohalides.
5

G. Varga, et al.
MolecularCatalysis493(2020)111072
Fig. 5. Ullmann-type CNe coupling reaction
between chlorobenzene and aqueous ammonia.
Reaction conditions: 1.0 mmol of aqueous
ammonia; 0.5 mmol of chlorobenzene; 0.04
mmol (0.06 mmol in the homogeneous case) of
catalyst; 0.5 mmol of base; 3.0 ml of solvent;
0.05 mmol of organic additive (hydroxy–L-
proline, if it is necessary).
Table 1
Scope of CuIBiOI catalyzed coupling reaction of
aryl halides and aqueous ammoniaa.
Reactant
Yield (%)
100
100
100
76
79
85
Fig. 6. Recyclability of the as-prepared CuIBiOI material tested in Ullmann-type
CNe coupling reaction between chlorobenzene and aqueous ammonia. The
optimized conditions: 1.0 mmol aqueous ammonia; 0.5 mmol chlorobenzene;
0.04 mmol catalysts; 0.5 mmol K3PO4; 3 ml EtOH/water (1:1; v/v%); T =80 °C;
t =20 h.
100
98
conversion from the vicinity of 100 % (Fig. S7) [93]. Fortunately, the
obtained results were in line with previously concluded statement.
The reaction was extended to various aromatic halides using mostly
the above-described optimum conditions (Table 1). The N-containing
heterocycles and anthracene derivative only required lengthening the
reaction time. The newly synthesized CuIBiOI catalyst proved to be
efficient with all the probe molecules. Interestingly, the presence of
electron-withdrawing groups was found to be more advantageous than
that of the electron-donating ones.
99
98
75*
4. Conclusions
In
this
study,
a
novel
mixed-cationic
material
of
71*
87*
Cu0.18Bi0.88O0.88 1.06
I
composition with somewhat distorted layered
structure with CuI ions in the layers was prepared, characterized and
used as efficient and selective catalyst for the Ullmann-type CNe cou-
pling reaction using green reaction conditions: H2O/ethanol solvent
mixture, no organic additive, mild reaction temperature and hetero-
geneous catalyst with excellent recycling ability.
Also, as an unexpected "side result", the catalytic activity of BiIII
cations in Ullmann-type reaction was demonstrated for the first time.
a
Reactions conditions: 1.0 mmol of aqueous
ammonia; 0.5 mmol of aryl halide; 0.04 mmol of
catalyst; 0.5 mmol of K3PO4; 3 ml of EtOH/water
(1:1; v/v%); T =80 °C; t =20 h.
Authors statement
* Reaction time: 40 h; +: determined by NMR.
All the authors contributed significantly to the manuscript.
G. Varga and M. Kocsis were involved in the catalyst synthesis and
catalytic testing part.
part of the manuscript.
I. Pálinkó conceptualized and supervised the project, wrote the final
version of the manuscript and did the revision.
G. Varga wrote the first draft of the manuscript.
A. Kukovecz, Z. Kónya, Igor Djerdj and P. Sipos were involved in the
instrumental characterization part and in putting together the relevant
6

G. Varga, et al.
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Declaration of Competing Interest
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Appendix A. Supplementary data
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