Nickel (II) dibenzotetramethyltetraaza[14]annulene supported on DFNS nanoparticles catalyst in carbonylative sonogashira coupling

Article abstract of DOI:10.1016/j.inoche.2020.108441

In this study, the carbonylative sonogashira coupling reaction was performed in the presence of CO (2 MPa) and Nitmtaa?DFNS as NPs. Nickel(II)dibenzotetramethyltetraaza[14]annulene complex (Nitmtaa) prepared and immobilized on amino-fucntionnalized DFNS (N-DFNS) via Ni[sbnd]N (NH₂) bond to obtain a stable and reusable new nanocatalyst named as Nitmtaa?DFNS. Good to superb performance products were provided deploying Nitmtaa?DFNS nanocatalyst. In addition, the anatomy of Nitmtaa?DFNS has been distinguished by various methods, including XRD, VSM, FT-IR, SEM, EDX, TEM, and TGA. In addition, the hot filtration test provided complete insight into the heterogeneity of the catalyst. The reuse and recycling of the catalyst were repeatedly investigated for coupling reactions. In addition, the mechanism of the coupling reactions was thoroughly studied.

Full text of DOI:10.1016/j.inoche.2020.108441

Inorganic Chemistry Communications 125 (2021) 108441
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Short communication
Nickel (II) dibenzotetramethyltetraaza[14]annulene supported on DFNS
nanoparticles catalyst in carbonylative sonogashira coupling
,
Shaopeng Tiana *, Qianqian Yangb, Seyed Mohsen Sadeghzadehc
a Xi’an Key Laboratory of Advanced Photo-electronics Materials and Energy Conversion Device, School of Science, Xijing University, Xi’an, Shaanxi 710000, China
b Fundamental Education Center, Xijing University, Xi’an, Shaanxi 710000, China
c Department of Chemistry, Faculty of Sciences, Neyshabur Branch, Islamic Azad University, Neyshabur, Iran
A R T I C L E I N F O
A B S T R A C T
Keywords:
In this study, the carbonylative sonogashira coupling reaction was performed in the presence of CO (2 MPa) and
Nitmtaa@DFNS as NPs. Nickel(II)dibenzotetramethyltetraaza[14]annulene complex (Nitmtaa) prepared and
Nanocatalyst
Green chemistry
Carbon monoxide
Nickel
–
immobilized on amino-fucntionnalized DFNS (N-DFNS) via Ni N (NH2) bond to obtain a stable and reusable
new nanocatalyst named as Nitmtaa@DFNS. Good to superb performance products were provided deploying
Nitmtaa@DFNS nanocatalyst. In addition, the anatomy of Nitmtaa@DFNS has been distinguished by various
methods, including XRD, VSM, FT-IR, SEM, EDX, TEM, and TGA. In addition, the hot filtration test provided
complete insight into the heterogeneity of the catalyst. The reuse and recycling of the catalyst were repeatedly
investigated for coupling reactions. In addition, the mechanism of the coupling reactions was thoroughly studied.
Carbonylative sonogashira
1. Introduction
dendritic, nanoflower, lamellar, and dandelion. In this study, to prevent
confusion, we used the name employed in the respective original works.
Carbonylative Sonogashira reaction is the most facile synthetic
method to generate alkynones by bonding terminal alkynes with carbon
monoxide and vinyl or aryl halides [1–3]. This reaction has a robust
power in organic synthesis and allows the production of biologically
active molecules. Alkynones could be employed in the synthesis of fur-
anones, pyrazoles or pyrroles [4]. The first sample of carbonylative
Sonogashira bond with palladium catalyst was announced in 1981 [5].
Like Sonogashira coupling, Pd nanocatalyst can be used in this reaction
in the attendance of copper co-catalyst [1–3]. Nevertheless, Cu-free
systems were also announced [1–3]. Alkynones could be produced by
deploying carbon monoxide gas or other carbon monoxide donors, like
Mo(CO)6, or formic acid [6–8]. These modified methods prevent toxic
carbon monoxide.
However, to maintain consistency, we use dendritic fibrous nanosilica as
a common name for this family of materials. The uniform roots of DFNS
roots in their dendritic fibrous morphology are more accessible in all
dimensions and sides in comparison with the tubular pores of SBA-15
and MCM-41. This fibrous structure increases the active sites like
metal oxides, metals, organic molecules, and organometallics in the
outer layer of silica without blocking the channels. In addition, it allows
more access to generated active sites. By modifying the particle size
(40–1120 nm) and density of fiber (number of fibers into one sphere),
the DFNS outer layer area may alter from 450 to 1244 m2 gꢀ 1 [16]. It
should be noted that unlike the erratic distribution of pores in usual
silica materials, DFNS has oriented fibrous channels that increase in size
from the center to the external layer. Controlling DFNS fiber density can
adjust the volume and size of the pores. Its adjustable pore size in the
range of 3.7–25 nm allows pores to fit the particular visitant molecules
in different sizes, whilst its adjustable pore volume of 2.18 cm3 gꢀ 1 fa-
cilitates the high loadings of visitants [17,18]. Visitants include organ-
ometallic complexes, organic molecules, metals, inorganic salts,
peptides, metal oxides, enzymes, proteins, carbon, and polymers. The
integrated porosity of DFNS accompany with its hierarchical pore
arrangement including mesopores of various sizes (such as suitable
As for morphology-controlled nanomaterials, dendritic fibrous
nanosilica has been recently discovered by Polshettiwar et al. [9–11]. It
depicted exceptional activities in all areas, including gas adsorption,
catalysis, energy storage, solar-energy harvesting, biomedical applica-
tions and sensors. It is called dendrimeric silica fibers morphology
(DFNS) considering the fibrous morphology reported in our previous
report [12–15]. Since the fibers were thin sheets 3.5–5.2 nm thick, other
names are deployed in the literature, including wrinkled, fibrous,
* Corresponding author.
E-mail address: tspxijing@163.com (S. Tian).
https://doi.org/10.1016/j.inoche.2020.108441
Received 10 December 2020; Received in revised form 30 December 2020; Accepted 30 December 2020
Available online 5 January 2021
1387-7003/© 2020 Elsevier B.V. All rights reserved.

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
Scheme 1. Carbonylative sonogashira coupling of terminal alkynes with aryl iodides in the attendance of Nitmtaa@DFNS NPs.
Scheme 2. Preparation of Nitmtaa@DFNS nanocatalyst.
amounts of macr- and microopores) helps the visitant molecules to
efficiently adsorb and diffuse in the fibrous spheres with minimal con-
straints; it helps to increase the accessibility of active sites and the
internallayer (a significant issue in usual mesoporous materials). Mac-
ropores contribute to the effective initial diffusion/adsorption of guest
molecules and DFNS have proper stability (mechanical, chemical, hy-
drothermal, and thermal) toward usual mesoporous materials, which is
a major concern due to their thin silica walls. DFNS is biocompatible as
well as nontoxic. Particle size control facilitates partial modification of
dispersion and realization of these nanospheres.
matrix by sol-gel process and its investigation in the epoxidation of
cyclooctene using PhIO as oxygen donor. However, the reaction was
notably slow with low conversion and high Nitmtaa leaching [22].
The current study reports the novel green approach for the synthesis
of DFNS NPs immobilized by Nitmtaa supported in amino, as dibenzo-
tetramethyltetraaza[14]annulene is a medium-hindrance amine with
cage-like anatomy. This anatomy was utilized as a cheap, green, highly
reflexive, and non-poisonous catalyst for Nitmtaa. The findings illus-
trated the influence of complex on the nano anatomies and character-
istics. This catalyst has many advantages, including facile separation,
good activity, and selectivity to activate CO under mild situations. This
study reports the first sample of the deployment of Nitmtaa@DFNS
catalyst in the carbonylative sonogashira reaction (Scheme 1).
One of the most known derivatives of dibenzotetraaza(14)annulenes
is Ni (II)dibenzotetramethyltetraaza[14]annulene. While Ni (II)diben-
zotetramethyltetraaza[14]annulene was already synthesized and char-
acterized by Goedken (1973) and Jaeger (1969) [19–21] to the best of
our knowledge, it has never been employed successfully as a catalyst
until now. Caiut et al. reported the encapsulation of Nitmtaa in alumina
2

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
Fig. 1. TEM pictures of (a) DFNS; and (b) Nitmtaa@DFNS NPs; SEM pictures of (c) DFNS; and (d) Nitmtaa@DFNS NPs.
2. Experimental
dried at 60 ◦C for 2 h.
2.1. A universal approach for providing DFNS nanoparticles
2.3. Synthesis of Nitmtaa@DFNS catalyst
Tetraethyl orthosilicate (TEOS) (3.5 g) was dissolved in a solution of
cyclohexane (40 mL) and 1-pentanol (3.0 mL). Then, a mixed solution of
cetylpyridinium bromide (CPB) (1.5 g) and urea (0.9 g) in H2O (45 mL)
was released and continually mixed for 45 min at room temperature.
Next, it was located in a Teflon-sealed hydrothermal reactor and heated
at 130 ◦C for 3 h. The generated silica was centrifuged then washed with
a mixture of deionized water and acetone, and oven-dried. The material
was then calcined in air at 600 ◦C for 6 h.
First, 3-aminopropyltriethoxysilane was sonicated in toluene (15
mL) for 40 min. Nitmtaa was prepared according to a procedure pub-
lished elsewhere. [23] The provided Nitmtaa (3.0 mmol) was then
released and the reaction was continued for 50 h under reflux situations.
Upon completion, the resulting precipitate was isolated employing by
filteration and washed with 15 mL of ethanol to eliminate the unreacted
Nitmtaa. The resulting solids were dried at r.t. and employed as the
catalyst in providing quinazolinone derivatives.
2.2. A universal approach for providing DFNS/3-
aminopropyltriethoxysilane nanoparticles
2.4. A universal approach for carbonylative sonogashira coupling
Aryl boronic acid (1.0 mmol), aryl iodide (1.0 mmol), Nitm-
taa@DFNS (6 mg), DMF (10 mL) and K3PO4 (5 mmol) were released to a
100 mL autoclave. The autoclave was closed, purified twice with carbon
monoxide gas, pressurized with 2 MPa of carbon monoxide, and then
heated under reflux for 4 h. Then, the reaction blend was cooled to room
temperature and the remaining CO gas was carefully evacuated and the
A solution of 3 mmol of DFNS NPs and 30 mL tetrahydrofuran was
made in a beaker, and then 30 mmol of NaH was released by ultra-
sonication. 30 mmol 3-aminopropyltriethoxysilane was dispersed drop-
wise at r.t. and mixed for another 13 h at 75 ◦C. The final products were
washed with ethanol and deionized water, respectively, and vacuum-
3

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
Fig. 2. FTIR spectra of (a) DFNS; (b) Nitmtaa@DFNS NPs.
Fig. 3. TGA diagram of (a) Nitmtaa, (b) N-DFNS, and (c) Nitmtaa@DFNS NPs.
Fig. 4. XPS spectra of Nitmtaa@DFNS NPs.
reactor was opened. The reaction was monitored by TLC. Upon
completion, ethanol was released to the reaction blend and the catalyst
was isolated by filtration. Then the solvent was eliminated from the
solution under decreased pressure and the final product was purified by
recrystallization employing ethyl acetate/n-hexane.
3. Results and discussion
The synthesis of Nitmtaa@DFNS NPs was a multi-step process. The
fibers of DFNS has several Si-OH groups on the outer layers. Therefore,
the DFNS rapidly functionalized with 3-aminopropyltriethoxysilane and
4

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
–
–
–
–
related to the different (C H) bonds like N CH2, CH2 CH2 and C H
emerged at 2899, 2974, 3060 cmꢀ 1. These observations affirmed that
the silica-coated outer layer of the DFNS was strongly altered with the
dibenzotetramethyltetraaza[14]annulene.
Fig. 3a shows the obtained TGA curve for the Nitmtaa. As can be
observed under the temperature range from 95 ◦C to 400 ◦C, there is a
one-step decomposition pattern. Organic weight reductions (in range of
200–410 ◦C) of N-DFNS and Nitmtaa@DFNS NPs are 14% and 21%,
respectively (Fig. 3b and c). The organic group functionalized analogs N-
DFNS and Nitmtaa@DFNS experienced notable weight loss, possibly
because of ligand decomposition.
We utilized XPS to examine the chemical sections on the Nitm-
taa@DFNS NPs level. Fig. 4 shows a scheme of XPS for the gathered
catalyst. Peaks Si, C, O, N, and Ni can be seen and the attendance of N 1s
additional affirms that DFNS were functionalized employing dibenzo-
tetramethyltetraazar[14]annulene. This shows the presence of diben-
zotetramethyltetraaza[14]annulene in the catalyst. Fig. 5 illustrates the
origins of the catalyst that was specified by EDX analysis. Fig. 5 illus-
trates the elements in Nitmtaa@DFNS NPs such as nitrogen, silicon,
oxygen, carbon, and nickel. The XRD patterns of DFNS NPs, and Nitm-
taa@DFNS NPs catalyst were shown in Fig. 6. The broad peak between
20◦ and 30◦ corresponds to amorphous silica (Fig. 6a). Fig. 6b shows a
typical XRD pattern of the Nitmtaa@DFNS NPs. The NPs outer layer
roughness was determined by AFM (atomic force microscopy) analysis.
Fig. 7 illustrates the topographic scheme. The higher altitude region,
shown in bright yellowish white, was increased by reducing T/W. This
Fig. 5. EDX spectra of Nitmtaa@DFNS NPs.
produced DFNS/3-aminopropylsilane NPs. Then, with Nickel(II)diben-
zotetramethyltetraaza[14]annulene complex (Nitmtaa) support on
DFNS/3-aminopropylsilane nanoparticles, Nitmtaa@DFNS catalyst was
synthesized in a simple and cheap procedure that is characterized by
easy access to active sites and high catalytic activity (Scheme 2).
The anatomies of the synthesized DFNS, and Nitmtaa@DFNS NPs
were investigated by SEM and TEM. The DFNS microspheres with
fibrous anatomy were identical and monodispersed (Fig. 1a). The
average diameter of the microspheres was about 2550–300 nm. TEM
and SEM pictures (Fig. 1a and c) further illustrate that the two fibers
were approximately 10–20 nm apart. The SEM pictures of Nitm-
taa@DFNS NPs show that rectification did not change the morphology
of DFNS (Fig. 1b and d); however, discrete nanospheres grew as twins.
FT-IR spectroscopy was deployed to discover the changes in the level
of the synthesized catalyst (Fig. 2). The bands at 796, 1084, and 1664
cmꢀ 1 in the FT-IR spectrum of both DFNS and Nitmtaa@DFNS corre-
–
– –
O Si
sponds to the tensile state of typical silanol group (Si OH), Si
vibrations, and the water absorbed on the solid outer layer, respectively
(Fig. 2a and b). Robust absorption bands at 1615 and 1458 cmꢀ 1 were
Fig. 7. 3D AFM cultivars of Nitmtaa@DFNS NPs.
–
–
differentiated from C N and C C vibrations of the dibenzote-
tramethyltetraaza[14]annulene section. The absorption bands were
Fig. 6. XRD analysis of (a) DFNS; (b) Nitmtaa@DFNS NPs.
5

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
Table 1
Anatomical parameters of DFNS, and the Nitmtaa@DFNS NPs.
Catalysts
SBET (m2 gꢀ 1
)
Va (cm3 gꢀ 1
)
DBJH (nm)
DFNS
634
299
3.2
1.7
11
8
Nitmtaa@DFNS
Table 2
Carbonylative Sonogashira coupling reaction by Nitmtaa@DFNS NPs with
different solvents and bases at different timesa.
Entry
Solvent
Base
Time (h)
Yield (%)b
1
H2O
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
–
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
4.0
3.0
–
2
EtOH
–
Fig. 8. Influences of enhancing the quantity of Nitmtaa@DFNS NPs on the
3
MeOH
i-PrOH
Toluene
n-Hexane
Dioxane
CH2Cl2
CHCl3
EtOAc
DMSO
CH3CN
THF
–
carbonylative sonogashira coupling.
4
–
5
–
6
–
7
–
8
51
49
60
47
64
56
74
93
–
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Anisole
DMF
solvent-free
DMF
–
DMF
CsF
33
52
8
DMF
Na2CO3
Et3N
DMF
DMF
NaOAc
KOH
17
31
32
44
24
93
82
DMF
DMF
Cs2CO3
K2CO3
tBuOK
K3PO4
K3PO4
DMF
DMF
DMF
DMF
Fig. 9. The influence of carbon monoxide pressure on the efficiency of car-
a
bonylative sonogashira coupling reaction.
Reaction situations: iodobenzene (1.0 mmol), phenylacetylene (1.0 mmol),
Nitmtaa@DFNS NPs (10 mg), base (5 mmol), solvent (10 mL), with 2 MPa of CO
and heated under reflux.
b
Isolated yields.
was relatively moderate. However, a low yield carbonylative cross-
coupling product was acquired in polar solvents. It was discovered
that conventional heating under DMF is more efficient than the utili-
zation of organic solvents. It is well known that bases are key elements in
coupling reactions; therefore, the reaction was performed in the atten-
dance of different organic and inorganic bases. Findings showed that the
most commonly deployed base K3PO4 was the most efficient in creating
carbonylative cross-coupling product. The reaction progress was moni-
tored by GC for the shortest required time in the attendance of 10 mg of
Nitmtaa@DFNS NP. Under the optimal situations, the superb efficiency
of carbonylative Suzuki coupling reaction could be acquired in 4.0 h.
We investigated the critical influence of temperature in the carbon-
ylative sonogashira coupling in the attendance of Nitmtaa@DFNS as a
catalyst. The finest temperature for this reaction was reflux heat that
alters the reaction efficiency, indicating that the catalytic activity is
sensitive to the reaction temperature. Catalyst loading is another key
element in the carbonylative cross-coupling reaction (Fig. 8). As can be
seen in Fig. 8, the yield was low in the nonattendance of catalyst.
Employing 1–6 mg of Nitmtaa@DFNS NPs in the sample reaction
resulted in good efficiencies of carbonylative sonogashira coupling re-
action. The finest outcome was achieved in the attendance of 6 mg of
Nitmtaa@DFNS NPs. Increasing the amount of catalyst did not lead to
any improvement, and no product was achieved in the nonattendance of
indicated an enhancement in the unevenness of the catalyst’s outer
layer.
N2 adsorption-desorption isotherm analysis was performed to
investigate the particular outer layer area and porosity of the products.
Following the BJH approach, the mean pore diameter, the particular
outer layer area, and the total pore volume values were determined
(Table 1). The BET findings illustrated that the active outer layers of the
DFNS and Nitmtaa@DFNS are 634 and 299 m2 gꢀ 1, respectively. The
results demonstrated that the specific outer layer reduced after Nitmtaa
intercalation. Moreover, the pore volume and average pore radius
reduced by employing Nitmtaa. Nitmtaa intercalation was found to have
more porous network anatomy.
To improve the reaction situations, the carbonylative cross-coupling
reaction of phenylacetylene with iodobenzene in the attendance of
Nitmtaa@DFNS was selected as an experimental model. The effect of
different parameters like time, base, and solvent (Table 2) on the model,
and the effect of solvents on the coupling reaction of carbonylative
Suzuki was examined. Findings illustrated that polar protic solvents
such as water, ethanol, isopropanol, and methanol, do not produce good
product efficiency. The efficiency of the cross-coupling product in polar
aprotic solvents, like THF, DMSO, CHCl3, EtOAc, CH3CN, and CH2Cl2
6

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
Table 3
Nitmtaa@DFNS NP-catalyzed carbonylative Sonogashira coupling of aryl iodides to phenylacetylene.a
Entry
1
Iodobenzene
Product
Yield (%)b
83
79
86
81
76
80
96
95
2
3
4
5
6
7
8
9
91
a
Reaction situations: phenylacetylene (1.0 mmol), aryl iodides (1.0 mmol), Nitmtaa@DFNS (6 mg), K3PO4 (1.0 equiv), CO (2.0 MPa), and DMF (5 mL) under reflux
for 4 h.
b
Isolated yield.
7

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
(Table 3, entry 9) that bear a methyl group on the ortho or para posi-
tions of the benzene ring, were deployed under optimized reaction sit-
uations. The favored products were achieved at 95 and 91% efficiencies,
respectively.
Table 4
Influence of different catalysts for carbonylative Sonogashira coupling of aryl
iodides to phenylacetylene.
Entry
Catalyst
Yield (%)a
For further study the performance of the catalyst, various control
exams are done and the achieved data was determined in Table 4.
Firstly, a standard reaction is performed by utilizing DFNS and 3-amino-
propyltriethoxysilane indicated that any value of the proper product is
not made after 4 h of reaction time (as can be seen in Table 4, entries 1
and 2). The DFNS and 3-aminopropyltriethoxysilane not provide the
satisfactory catalytic activity in mild conditions of reaction. It is
important to note that there is not high distinct in the reaction products
while reaction is performed by utilizing Nitmtaa@DFNS as well as
Nitmtaa NPs catalyst (as can be observed in Table 4, entries 3 and 4).
Our results indicate that the cycle of reaction is basically catalyzed using
Nitmtaa sorts supported on the nanostructure of DFNS. In addition,
Nitmtaa could not be used or recovered for the next runs. It is also
determined that Nitmtaa@DFNS NPs are utilized in the subsequent
studies due to its high reactivity and selectivity as well as simple
separation.
1
2
3
4
DFNS
–
3-aminopropyltriethoxysilane
Nitmtaa@DFNS
Nitmtaa
–
93
92
a
Isolated yield.
The reusability characteristic of a catalyst is considered as a key
characteristic in green chemistry. Hence, the reusability of NPs of the
Nitmtaa@DFNS was examined in optimal moods for carbonylative
sonogashira coupling reaction. Upon completion of the reaction, the
Nitmtaa@DFNS solid NPs were removed readily (fora few seconds).
Fig. 10 shows ten consectiuve runs of using the catalyst. The product
yield was 89%, which shows merely a 4% drop.
Fig. 10. Recyclability of the catalyst.
Finally, we conducted a leaching experiment to examine the homo-
genety of the catalyst system. The reaction was initially performed
employing optimized situations, in the attendance of the ten-times
recycled catalyst. After 2 h of reaction time, the catalyst was isolated
by hot filtration and the solution was mixed for an additional 2 h. Fig. 11
depicts the carbonylative sonogashira coupling reaction as a function of
time with the ten-times recycled catalyst (blue curve). As can be seen,
the use of reagent was no longer observed after the removal of the
catalyst (green curve).
The SEM and TEM image analysis illustrated the higher numbers of
the fibrous nanoparticles of Nitmtaa@DFNS. Fig. 12a and b depict the
SEM and TEM pictures of the new fibrous nanoparticles of Nitm-
taa@DFNS, and the ten-times recycled Nitmtaa@DFNS. The fibrous
anatomy of the catalyst was still visible after ten reuses and did not differ
from fresh nanoparticles after ten consecutive uses. This can be attrib-
uted to strong recyclability. Moreover, the thermal stability of the
recycled Nitmtaa@DFNS catalyst was not as good as the fresh catalyst
after ten uses. This may be due to the loss of Nitmtaa in DFNS fibers
during recycling (Fig. 13). Fortunately, its performance does not change
at 100 ◦C.
Fig. 11. Leaching test for the catalyst of carbonylative sonogashira coupling.
the catalyst. The influences of CO pressure in the attendance of iodo-
benzene, phenylacetylene, and Nitmtaa@DFNS NPs for 4 h are depicted
in Fig. 9. Catalyst blend achieved an efficiency of 93% at 2 MPa pressure.
In all experiments, no obvious by-products were obtained by GC and
carbonylative sonogashira coupling reaction was performed with a yield
of 93%.
4. Conclusions
In summary, a novel class of DFNS was reported with support for
Nitmtaa, which exhibits tremendous catalytic activity for carbonylative
sonogashira coupling in excellent efficiency. SEM, TEM, FTIR, XPS, ICP-
MS, BET, TGA, and EDX indicated the functionalization of Nitmtaa in the
outer layer of the mesopores silica. Moreover, the catalyst was reusable
and easily recoverable. Such a logical design for single-site catalysts
with full employment of any Nitmtaa active site, superb reusability, and
insignificant catalyst leaching are consistent with the concepts of green
chemistry. Therefore, the study of Nitmtaa@DFNS may create a poten-
tial basis for the fabrication of other readily available nanocatalyst that
would be robustly efficient in different nanocatalyst-based reactions.
This process might lead to the production of nanocatalysts with desir-
able characteristics, including efficiency and ease of reuse.
The carbonylative sonogashira coupling reactions of phenyl-
acetylene with aryl iodides were done under optimal situations, and the
findings are presented in Table 3. The reactions of phenylacetylene with
aryl iodides progressed slowly to provide the favored products in
76–86% yields (Table 3, rows 1–6). Significantly, the halogen atoms (I,
Br, and Cl) attached to the benzene rings of the substrates were pre-
served in the anatomies of the products, suggesting that further modi-
fications may lead to beneficial compounds. Reactions of aryl iodides
that pose robust electron-withdrawing groups like cyano (NC) and tri-
fluoromethyl (CF3) at the para position, provided relatively good effi-
ciencies (76, and 80%). Superb efficiencies were obtained when 1-iodo-
4-methylbenzene (Table 3, entry 8) and 1-iodo-2-methylbenzene
8

S. Tian et al.
Inorganic Chemistry Communications 125 (2021) 108441
Fig. 12. (a) TEM, and (b) FE-SEM pictures of the improved Nitmtaa@DFNS NPs after the tenth run for carbonylative sonogashira coupling.
Foundation of China (21706218), the Natural Science Foundation of
Shaanxi Province (2019JQ-920) and the Youth Innovation Team of
Shaanxi Universities.
References
[1] X.F. Wu, H. Neumann, M. Beller, Chem. Soc. Rev. 40 (2011) 4986–5009.
[2] X. Feng, J. Song, M. Bao, J. Chin. Chem. Soc. 65 (2018) 337–345.
[3] S.T. Gadge, B.M. Bhanage, RSC Adv. 4 (2014) 10363–10367.
[4] X.F. Wu, H. Neumann, M. Beller, Chem. Rev. 113 (2013) 1–35.
[5] T. Kobayashi, M. Tanaka, J. Chem. Soc. Chem. Com. 333–334 (1981).
[6] L. Akerbladh, P. Nordeman, M. Wejdemar, L.R. Odell, M. Larhed, J. Org. Chem. 80
(2015) 1464–1471.
[7] X. Qi, L.-B. Jiang, C.-L. Li, R. Li, X.-F. Wu, Chem. Asian J. 10 (2015) 1870–1873.
[8] M. Iizuka, Y. Kondo, Eur. J. Org. Chem. (2007) 5180–5182.
[9] V. Polshettiwar, D. Cha, X. Zhang, J.M. Basset, Angew. Chem. 49 (2010)
9652–9656.
[10] A. Maity, V. Polshettiwar, ChemSusChem 10 (2017) 3866–3913.
[11] P.K. Kundu, M. Dhiman, A. Modak, A. Chowdhury, V. Polshettiwar,
ChemPlusChem 81 (2016) 1142–1146.
[12] P. Gautam, M. Dhiman, V. Polshettiwar, B.M. Bhanage, Green Chem. 18 (2016)
5890–5899.
[13] A. Fihri, D. Cha, M. Bouhrara, N. Almana, V. Polshettiwar, ChemSusChem 5 (2012)
Fig. 13. TGA of the fresh Nitmtaa@DFNS catalyst (a) and the recycled Nitm-
85–89.
taa@DFNS catalyst after 10 times reusing (b).
[14] S.M. Sadeghzadeh, J. Mol. Catal. A: Chem. 423 (2016) 216–223.
[15] S.M. Sdeghzadeh, Catal. Sci. Technol. 6 (2016) 1435–1441.
[16] S.M. Sadeghzadeh, Catal. Commun. 72 (2015) 91–96.
[17] S.M. Sadeghzadeh, Green Chem. 17 (2015) 3059–3066.
[18] Z. Dong, X. Le, X. Li, W. Zhang, C. Dong, J. Ma, Appl. Catal. B 158–159 (2014)
129–135.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
[19] E.G. Jaeger, Z. Anorg, Allg. Chem. 364 (1969) 177.
[20] V.L. Goedken, J. Molin Case, Y.-A. Whang, J. Chem. Soc., Chem. Commun. (1973)
337.
[21] V.L. Goedken, J.J. Pluth, S.-M. Peng, B. Bursten, J. Am. Chem. Soc. 98 (1976) 8014.
[22] J.M.A. Caiut, S. Nakagaki, O.J. De Lima, C. Mello, C.A.P. Leite, E.J. Nassar, K.
J. Ciuffi, H.C. Sacco, J. Sol-Gel, Sci. Techn. 28 (2003) 57–64.
[23] M. Abboud, T. Sahlabji, M. Eissa, R. Bel-Hadj-Tahar, A.T. Mubarak, N. Al-Zaqri, M.
S. Hamdy, New J. Chem. 44 (2020) 20137–20147.
Acknowledgement
This work were supported by the National Natural Science
9