PdO nanoparticles supported on triazole functionalized porous triazine polymer as an efficient heterogeneous catalyst for carbonylation of aryl halides

Article abstract of DOI:10.1002/aoc.4994

A well-defined triazole functionalized porous triazine based polymers act as solid heterogeneous catalyst after incorporating palladium oxide nanoparticles (PdO@TTAS) have been synthesized and thoroughly characterized by various techniques such as, FT-IR, UV-DRS, solid state ¹³C CP-MAS, XPS, powder X-ray diffraction, TGA, SEM and TEM analysis has been detailed illustrated. It is important to note that synthesized catalytic performance for carbonylation of aryl halides (X?=?I, Br) with EDC.HCl (N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride), and formic acid was found to be an effective CO source in the presence of triethylamine as a base and DMF as a solvent medium at 80?°C for about 3?hr. The PdO@TTAS catalyst exhibits superior catalytic performance and along with good yield (up to 90%). Moreover, studying the heterogeneity and reusability of the environmentally friendly solid catalyst can be easily separated by simple filtration and then recycled for several times. In this reaction method, we avoided ligand, additive, promoters and CO gas, due to additional problem arise by using gaseous CO, highly toxic greenhouse gases and high pressurized reaction setup.

Full text of DOI:10.1002/aoc.4994

Received: 25 February 2019
DOI: 10.1002/aoc.4994
Revised: 19 April 2019
Accepted: 23 April 2019
F U L L P A P E R
PdO nanoparticles supported on triazole functionalized
porous triazine polymer as an efficient heterogeneous
catalyst for carbonylation of aryl halides
Velu Sadhasivam | Rajendran Balasaravanan | Ayyanar Siva
Supramolecular and Organometallic
A well‐defined triazole functionalized porous triazine based polymers act as
Chemistry Lab, Department of Inorganic
Chemistry, School of Chemistry, Madurai
solid heterogeneous catalyst after incorporating palladium oxide nanoparticles
Kamaraj University, Madurai‐625021,
Tamil Nadu, India
(PdO@TTAS) have been synthesized and thoroughly characterized by various
techniques such as, FT‐IR, UV‐DRS, solid state 13C CP‐MAS, XPS, powder X‐
Correspondence
Ayyanar Siva, Supramolecular and
ray diffraction, TGA, SEM and TEM analysis has been detailed illustrated. It
is important to note that synthesized catalytic performance for carbonylation
Organometallic Chemistry Lab,
Department of Inorganic Chemistry,
School of Chemistry, Madurai Kamaraj
University, Madurai‐625021, Tamil Nadu,
India.
of aryl halides (X = I, Br) with EDC.HCl (N‐(3‐dimethylaminopropyl)‐N′‐
ethylcarbodiimide hydrochloride), and formic acid was found to be an effective
CO source in the presence of triethylamine as a base and DMF as a solvent
medium at 80 °C for about 3 hr. The PdO@TTAS catalyst exhibits superior cat-
alytic performance and along with good yield (up to 90%). Moreover, studying
the heterogeneity and reusability of the environmentally friendly solid catalyst
can be easily separated by simple filtration and then recycled for several times.
In this reaction method, we avoided ligand, additive, promoters and CO gas,
due to additional problem arise by using gaseous CO, highly toxic greenhouse
gases and high pressurized reaction setup.
Email: drasiva@gmail.com; siva.
chem@mkuniversity.org
KEYWORDS
CO insertion, covalent organic framework, formic acid, Pd nanoparticle, solvothermal
1 | INTRODUCTION
research fields, such as gas adsorption,[5] gas storage,[6]
photocatalyst,[7,8] solarcells,[9] chemosensing,[10,11] gas
Over the past few decades, there has been exponential
development in the field of functionalized porous cova-
lent organic frameworks (COFs), these COFs materials
have been constructed by purely organic building unit
via strong covalent bonds,[1–4] due to their some textural
properties and potential in diverse applications such as
high specific surface area, high thermal and chemically
stable and large micropore volumes with π‐columnar
structure, cost‐effective and modular synthetic procedure
to provide a large number of different polymeric architec-
tures. They exhibited large potential applications in many
separation,[12] water purification membranes,[13] chiral
catalyst,[14] and especially used for heterogeneous cata-
lyst.[15–19] In addition to that, porous COF materials are
not soluble in any other organic or aqueous medium,
highly stable in high‐boiling solvents. Hence, these COFs
materials are applicable to heterogeneous catalytic sys-
tem. Among several solid supports are used for catalytic
reaction. However, the nitrogen containing functional-
ized materials is an appropriate choice, because of various
benefits, including high surface area, functionalization
ability, high stability, and large amount of nitrogen
Appl Organometal Chem. 2019;e4994.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4994

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SADHASIVAM ET AL.
present in the supports, which is beneficial to immobilize
a large number of metal binding sites, which is enhancing
the high catalytic activity as well as the stability of the
supported materials.
shows some selectivity trouble to catalytic reaction with-
out solid supports. Hence we can choose the triazole
functionalized polymeric materials will act as good solid
supports high surface area and high amount of nitrogen
atom present in the polymeric networks.
Recently, metal oxide nanoparticles (NPs) have been
great attention for current research field and enhance
the catalytic activity in heterogeneous catalysis compared
with metal nanoparticles, due to their high catalytic prop-
erties and some potential applications, these metal oxides
nanomaterials have totally differ from bulk metal one,
there exists some previously reported literature evidence
showed that PdO nanoparticles have high catalytic per-
formance compared to Pd metallic nanoparticles. The
heterogeneous PdO nanoparticles was performed to the
reduction of 4‐nitrophenol,[20] Pd/PdO NPs supported
on carbon nanotubes are utilized to highly efficient cata-
lyst for promoting Suzuki‐Miyaura coupling reaction in
water medium,[21,22] Pd/PdO supported on porous
graphene as electrocatalyst for methanol oxidation,[23]
and Co3O4 nanosheet supported PdO/CeO2 catalysts are
used for methane combustion reactions.[24] In addition
to that, the PdO nanoparticles supported on functional-
ized polymeric materials act as heterogeneous catalysts
shows good catalytic activity and stability than that of
commercial available Pd/C catalyst and PdO catalyst
can enhance high catalytic activity.
Generally, aromatic aldehydes are structural motifs
present in agrochemicals, many natural products and
pharmaceuticals. Transition metal‐catalysed carbonylative
reactions have been focused extensive research in
laboratory‐scale, organic synthesis, including industrial
processes and medicinal applications.[25] Although, inser-
tion of carbon monoxide gas into an organic molecule
(known as carbonylation), it's a convenient but under
developed synthetic route to a number of common func-
tional groups including amides, esters, acids, lactams
and lactones.[26–28] This types of carbonylation reactions
are usually carried out at high pressures using carbon
monoxide gas in the presence of a palladium‐phosphine
catalyst, expensive ligands (X‐Phos, P‐Phos, Phanephos
and Bophoz) and can take many hours to completion
of the reactions (Scheme 1). Despite considerable
success, the major drawbacks associated with such
phosphines are environment pollutions and their
handling problems, inherent toxicity, difficulty in
handling toxic gaseous carbon monoxide, including its
storage and transport, represents real problems. Unfortu-
nately, such a disadvantage reduces the overall utility of
carbonylation. Furthermore, the alternative formylation
reagent like POCl3/DMF (Vilsmeier‐Haack reaction)
leads to formation of more reactive iminium adduct,
these reagents are widely used for synthetic organic
The functionalized covalent organic polymer have
been normally used as a metal nanoparticle supports for
the dispersion and stabilization of metal nanoparticles
due to high surface energy of free nanoparticles tend to
aggregate, unique physical properties, inherent size. It
SCHEME 1 Palladium‐catalyzed
carbonylative coupling reactions

SADHASIVAM ET AL.
3 of 17
chemistry, especially the formylation of electron rich
aromatics and olefins. However, these reagents are more
2 | RESULTS AND DISCUSSION
reactive
and
hazards,
stoichiometric
ratio
2.1 | Characterization of TTAS and
substrate/reagent (1:10), it's difficult to handle and large
amount of hydrochloric acid generated from POCl3, to
avoid the above difficulties and replace the direct use
of CO gas. In this respect, alternative CO sources have
been developed such as amoylstannanes,[29] transition
metal carbonylcomplexes,[30] N‐formylsaccharin,[31]
oxalyl chloride,[32] and carbamoylsilane.[33] Recently,
Xiao‐Feng Wu et al. reported the selective synthesis of
aldehydes and acids from aryl halides, formic acid as a
CO source in the presence of palladium catalysed and
ligands controlled.[34,35] Mohammad Mahdavi et al. also
reported the use of Mo (CO)6 as a solid CO precursor
in the Pd supported catalyzed gas‐free carbonylation‐
cyclization of N‐(2‐bromoaryl)benzimidamides reactions
has been reported. Furthermore, some of the research
groups have been reported for carbonylation reaction
using Pd (OAc)2 homogeneous catalyst and high cost
phosphine ligands were shown in comparison Table 4,
The homogeneous catalyst totally differ from heteroge-
neous catalyst, the homogeneous catalyst exhibits highly
soluble in solution phase and better activity, high selec-
tivity compared to the heterogeneous catalyst, these
types of catalysts and costly ligands have some practical
issues like recyclability and catalyst separation, deactiva-
tion via aggregation into Pd nanoparticles and also phos-
phine based ligands are highly toxic, hazards nature in
the environment pollutions. In this regards, we have
been developed phosphine ligand free and metal nano-
particles stabilized by melamine based solid supports,
hazards free, nontoxic, easily degradable for melamine
based solid supports, highly stable and insoluble in
organic/aqueous media, then effectively utilized to envi-
ronmental friendly heterogeneous catalysis applications.
In this present work, we wish to report our new achieve-
ment on this original idea, to synthesize triazole function-
alized covalent organic triazine polymer may immobilized
a large number of PdO nanoparticles and robust stability as
an efficient heterogeneous catalyst for carbonylation of
PdO@TTAS
A new triazole functionalized nitrogen containing TTA
(amine‐formaldehyde polymer), TTAS (triazole function-
alized polymer) and PdO@TTAS (PdO supported on tri-
azole functionalized polymers) was synthesized under
solvothermal conditions by condensation reaction
between 4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline and
formaldehyde, PEG/DMF (1:1) solvent in the presence
of 1 N NaOH at 140 °C for about 48 hr to obtain triazine
based polymeric supported materials (TAS). Furthermore,
the synthesized TAS were functionalized with the triazole
unit by using n‐bromoprop‐1‐yne and sodium azide in the
presence of triethylamine to obtained TTAS material,
After that, PdO‐NPs successfully incorporated into the
TTAS polymeric materials (PdO@TTAS).
The FT‐IR spectra of compound PdO@TTAS and cor-
responding intermediates are shown in Figure 1. The
absorption peak that occurs at 2890 cm−1 for all the three
corresponding materials TTA, TTAS and PdO@TTAS are
attributed to the aliphatic C‐H stretching frequency band
originating from methylene linkers between the two aro-
matic amine units, respectively. Furthermore, TTAS and
TTA contains secondary amine and 1,2,3‐triazole N‐H
stretching band observed at 3355 cm−1 and 3341 cm−1
respectively, based on this observed results, we suggested
that formaldehyde was successfully coupled with starting
material 4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline to pro-
vide triazole functionalized TTAS covalent organic poly-
meric materials. On the other hand, the weak
absorption band appeared at 2022 cm−1, 2209 cm−1 for
PdO@TTAS and TTAS, which is corresponding to
N=N=N‐ stretching bonds and acetylene C‐H stretching
frequency. It's strongly suggested that triazole ring suc-
cessfully functionalized into polymeric network. In addi-
tion to that, remaining all the stretching bands are
similar pattern observed and hence for all polymeric
materials does not show any changes in absorption posi-
tion, it is clearly represented that structural regularity is
well maintained after the synthesis of 1,2,3‐triazole func-
tionalized and incorporating Pd NPs.[43] Finally, the
appearance of PdO nanopartical was confirmed by
PdO@TTAS absorbance peaks appeared at 521 and
594 cm−1 are attributed to stretching vibrations of PdO
nanoparticles.[44]
aryl halides (X
= I, Br) using EDC.HCl (N‐(3‐
dimethylaminopropyl)‐N′‐ethylcarbodiimide hydrochlo-
ride) and formic acid as a CO source in the presence of
triethylamine and DMF solvent medium at 80 °C for about
3 hr. In this method EDC/HCl and HCOOH used as CO
source for the synthesis of desired product, which exhibits
high catalytic activity and excellent to good yield (up to
90%). To the best of our knowledge, there is no report
describing the carbonylative of aryl halide using
HCOOH/EDC.HCl and tiny amounts of PdO@TTAS
(15 mg) heterogeneous catalytic systems. The reaction
scheme is presented in Scheme 2.
The electronic spectra of TTAS and PdO@TTAS were
recorded in the range of 200–800 nm shown in
(Figure 2). It's provided further evidence for the presence
of PdO on polymeric supports. The TTAS and
PdO@TTAS both materials show three absorbance band

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SADHASIVAM ET AL.
SCHEME 2 Synthesis of PdO‐NPs supported on 1,2,3‐triazole functionalized porous triazine polymer networks (PdO@TTAS)
FIGURE
1
FT‐IR spectra of compound TTA, TTAS and
FIGURE 2 UV‐Diffused reflectance spectra of compound TTAS
PdO@TTAS
and PdO@TTAS
respectively. In addition to that, the PdO@TTAS shows
all types of transition bands were presented compared
with TTAS, which indicates the structural regularity was
well maintained after the synthesis of PdO NPs
appeared at 236, 310 and 400 nm, respectively. Which
corresponds to π‐π*, n‐π* transition of aromatic phenyl
moieties (C=C), core triazine (C=N), and ligand to metal
charge transition between metal and imine nitrogen,

SADHASIVAM ET AL.
5 of 17
incorporated into the TTAS polymeric materials. Further-
more, PdO@TTAS exhibited a broad absorbance band at
range of 500–800 nm due to the charge‐transfer transi-
tions of an electron excited from the triazole and triazine
nitrogen lone pair to a vacant d‐orbitals of the metallic
nanoparticles.[45] It's confirmed that PdO‐NPs success-
fully incorporated into the triazole functionalized poly-
meric supports.
The X‐rays diffraction measurement was used to deter-
mine the crystalline structure of synthesized polymeric
material, the powder X‐ray diffraction (PXRD) pattern of
TTA, TTAS and PdO@TTAS shows several peaks over a
wide diffraction peak at around the 2θ values 5.4°‐10.7°
and 15.3°‐26.8° (Figure 3), the set of the broad peak sug-
gested that synthesized covalent triazole polymer (CTPs)
materials (TTAS) amorphous nature and higher degree
of long range order. Further, the TTAS and PdO@TTAS
both materials are compared with TTA, similar pattern
and sharp new peaks was observed at around 2θ values
26.66°, 29.67° and 36.19° respectively, which indicates that
TTAS was well maintained after the synthesis of
PdO@TTAS. It's also confirmed by UV‐diffused reflec-
tance spectra. Furthermore, the newly prepared
PdO@TTAS polymeric materials having strong diffraction
peaks at around 2θ values 40.02°, 46.45° and 67.8°, it can
be attributed to the lattice planes of (111), (200) and
(220), respectively, which indicating that the well disper-
sion of PdO nanoparticles for face centered cubic (fcc) lat-
tice arrangement and palladium present in the Pd2+ state,
which consists with pervious reported literature.[46,47]
Thermal stability of triazole functionalized covalent tri-
azine polymeric material TTAS and PdO@TTAS has been
investigated via TGA from 30 °C to 800 °C at 10 °C/min
shown in Figure 4, thermal decomposition of TTAS shows
two distinct weight loss steps in the temperature range 35–
324 °C and 324–660 °C. The first 4% of weight loss observed
FIGURE 4 Thermogravimetric analysis of compound TTA,
TTAS and PdO@TTAS
at 65 °C, which may be assigned to volatilization and
vaporization of solvent/small molecules and the second
29% of weight loss observed at 250 °C which corresponds
to decomposition of starting material 4,4′,4″‐(1,3,5‐tri-
azine‐2,4,6‐triyl)trianiline. In addition to that, the
PdO@TTAS shows gradual weight loss takes place in a
temperature range of 250–554 °C. From the observed
results, it's confirmed that both materials TTAS and
PdO@TTAS stable up to 250 °C.
In order to confirm the chemical structure of TTAS was
performed by 13C solid state NMR spectroscopy (Figure 5).
The 13C cross‐polarization magic angle spinning (CP‐
MAS) NMR spectra of compound TTAS displayed ten res-
onances peak appeared at 170.44, 151.32, 131.36, 130.57,
126.01, 115.20, 110.40, 61.40, 37.10, 31.88 ppm, the pres-
ence of core triazine carbon resonate at 170.44 ppm,[48]
and the signal 151.32 ppm corresponds to triazine amine
quaternary carbon, whereas the signal appeared at
131.36, 130.57 and 61.40 ppm which were attributed to
the 1,2,3‐triazole carbons (‐CH) and allyl carbon (CH2),
thus the clearly demonstrated triazole function was suc-
cessfully incorporated in to the covalent triazine polymeric
(TTAS) networks. Furthermore, the signals appeared at
37.10 ppm aliphatic regions which can be assigned to the
methylene carbon. In addition to that, all the aromatic car-
bon appeared at 126.01, 115.20, 110.40 ppm. Based on the
obtained results, it is clearly confirmed that the condensa-
tion reaction between the 4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)
trianiline and formaldehyde were successfully polymer-
ized through methylene bridging units.[45,49]
The surface area and porosity of the PdO@TTAS were
measured using N2 adsorption–desorption isotherm tech-
nique at 77 K are shown in Figure 6. The Brunauer–
Emmett–Teller (BET) total surface area and total pore
volume was calculated to be 112.16 m2 g−1 and
FIGURE 3 Powder X‐ray analysis of compound TTA, TTAS and
PdO@TTAS

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SADHASIVAM ET AL.
FIGURE 5 13C CP‐MAS NMR
spectrum of compound TTAS
0.185 cm3 g−1 (P/Po = 0.987) respectively, (see SI Figure
S6) the pore size distribution was calculated using nonlo-
cal density functional theory (NLDFT), the PdO@TTAS
does not get uniform pore size. It shows the different pore
size was obtained 0.74, 0.93, 1.21 nm, which can be attrib-
uted to the synthesized material does not uniform and
ordered, layered structure and it's a micro porous
material.
In order to investigate the chemical structure, compo-
sition and element valence state of PdO@TTAS deter-
mined by XPS analysis are shown in Figure 7 and 8.
The obtained survey scans XPS spectrum of the
FIGURE 6 N2 adsorption (filled symbols) /desorption isotherm (empty symbols) and (b) Pore size distributions of PdO@TTAS
FIGURE 7 X‐ray photo electron spectrum of compound PdO@TTAS (a) Pd3d spectrum (b) C1s spectrum

SADHASIVAM ET AL.
7 of 17
compound PdO@TTAS catalyst represented in the pres-
ence of carbon, oxygen, nitrogen and palladium as the
constructing elements. The peak appeared at 337.6 eV,
342.9 eV are ascribe to the binding energy values of Pd
3d3/2 and Pd 3d5/2, respectively the binding energy values
separation of 5.3 eV between the 3d3/2 and 3d5/2, these
binding energy values are matched with pervious
reported literature.[50,51] Which had been proven to
FIGURE 8 X‐ray photo electron spectrum of compound PdO@TTAS (a) N1s core level spectrum (b) survey scans spectrum
FIGURE 9 SEM Images of compound (a) TTAS (b) PDO@TTAS

8 of 17
SADHASIVAM ET AL.
palladium present in the supported material as Pd2+ in
form of PdO nanoparticles. As shown in Figure 7b, the
XPS spectrum of C1s can be de‐convoluted into three
major peaks at 285.2, 286.9, 288.14 eV, respectively.
Which is corresponds to the binding energy of C‐C/C‐H
(Sp2), C‐N (Sp2) and C‐N (Sp3), these results are clearly
indicated that triazine triamine and formaldehyde are
thoroughly coupled by methylene bridged units to
obtained polymeric structure.[43,52] Furthermore, the
XPS spectrum of N1 s core level (Figure 8a) exhibits three
peaks at 399.5, 400.3 and 401.4 eV, respectively. It's attrib-
uted to the binding energy of C=N for triazine ring, ‐
N=N‐and N‐H for triazole ring nitrogen. The N1 s core
level clearly shows that triazole was successfully func-
tionalized into the porous triazine polymeric supported
materials.[53,54]
N (orange), and O (blue) elements and Pd (green) at dif-
ferent points in the porous triazine covalent organic poly-
mers (Figure 10) (See SI Figure S10).
The morphological structure of polymers and average
particle size of metal nanoparticles was determined by
using Transmission electron microscopy (TEM) which
shown in Figure 11. The TEM image of PdO@TTAS rep-
resents porous polymer structure and small black dots
were represented PdO NPs uniformly dispersed on TTAS
porous covalent triazine polymeric materials. Moreover,
the average particle size of dispersed palladium nano par-
ticles is around 2.89 nm.
2.2 | Catalytic studies of PdO@TTAS for
carbonylation of aryl halides
In order to investigate the morphological structure for
TTAS and PdO@TTAS were confirmed by SEM (scanning
electron microscopy) which are shown in Figure 9 and
(see SI Figure S8 & S9). The SEM images of both mate-
rials showed direct visualization of porous cross‐linked
structure with partially crystalline nature. The metal con-
tent of PdO@TTAS material was investigated using EDS
(Energy dispersive X‐ray spectroscopy) and elemental
mapping was also confirmed in the presence of C (pink),
Initially to check the catalytic activity of heterogeneous
catalyst PdO@TTAS for carbonylation of aryl halide reac-
tion was conducted using iodobenzene as a model sub-
strate and formic acids act as CO source in the presence
of EDC.HCl, triethylamine and DMF solvent at 80 °C,
the results are summarized in Table 1. From the table,
we observed that the reaction does not undergo in the
presence of TTAS, absence of catalyst PdO@TTAS and
FIGURE 10 Elemental mapping of compound PdO@TTAS, C (pink), O (blue), N (orange), Pd (green)

SADHASIVAM ET AL.
9 of 17
FIGURE 11 TEM images of compound PdO@TTAS
CO source. In these reactions clearly speculated that Pd
was playing a crucial role in the carbonylative reactions
(Table 1, entry 1 & 2). The reaction was conducted by var-
ious CO sources such as HCOOH/DCC, HCOOH/EDC.
HCl, CO gas, HCOOH/Ac2O, oxalic acid and
HCOOH/H2SO4, FeCl3/HCOOH investigated. Among the
various CO sources, the HCOOH/EDC.HCl to give the
highest amount of 90% yield was observed (Table 1, entry
3), and remaining CO sources gave a moderate yield of
benzaldehyde and minor amount of benzoic acid as
byproduct observed (Table 1, entries 6, 7, 8,12 and 29),
the reaction does not effectively undergoes in the presence
of Lewis acid FeCl3 to get red colour solution was observed
and CO gas does not effectively generated. Additionally,
no product was obtained for neither additive (EDC.HCl)
and nor CO source (HCOOH) investigated (Table 1,
entries 4, 5, 9, 10 and 11). Among all the tested solvents,
DMF provided to the best solvent (Table 1, entries 16–
19). Further, various bases were screened, when
triethylamine was applied as a base (Table 1, entry 3) to
provide 90% of yield. Other bases, including K2CO3, pyri-
dine (Py), and piperidine (Pip) provided the desired
product in lower yields (Table 1, entries 20–22). In addi-
tion, the reaction was performed with some hindrance
bases DIEPA and DIBACO to obtain moderate amount
of yield 64% and 40% (Table 1, entry 26, 27). Furthermore,
the carbonylative reaction was also carried out in the pres-
ence of some commercially available palladium catalysts
such as Pd (PPh3)4, PdCl2, Pd/C, Pd (OAc)2 and our goup
also synthesis palladium catalyst and reported instead of
PdO@TTAS, providing moderate yield of 68, 60, 50 and
75% (Table 1, entries 22–24 and Table 3). Finally, the reac-
tion temperatures, catalyst loadings, and the loading of
other additives and base were optimized as well, but no
significant improvement in the yields could be obtained.
Under optimised reaction conditions, we carried out the
various substrate scope using HCOOH/EDC.HCl with var-
ious substituted aryl halides (X = I, Br) was studied and the
obtained results are listed in Table 2, (entries 1–18). The
reaction was conducted with a wide range of substrates
containing both electron‐withdrawing and donating
groups substituted on bromobenzene gave corresponding
carbonylation products with excellent yield up to 90%
and high turnover number up to 2859 (Table 2, entry 1).

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SADHASIVAM ET AL.
TABLE 1 Optimization of PdO@TTAS‐Catalyzed formylation of aryl halide with CO source
Entry
Catalyst
Solvent
CO Source
Base
Temp. °C
Yield (%)
1
‐
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
H2O
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
NEt3
Pyr
80
80
80
80
80
80
80
80
80
80
80
80
60
90
100
80
80
80
80
80
80
80
80
80
80
80
80
80
80
NR
NR
90
2
TTAS
3
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
Pd (OAc)2
PdCl2
4
NR
NR
60
5
DCC
6
CO gas balloon
EDC.HCl/DCC
7
60
8
HCOOH/Ac2O
75
9
HCOOH/H2SO4
(COOH)2
NR
NR
NR
20
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
EDC.HCl
AcOH/EDC. HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
HCOOH/EDC.HCl
FeCl3/HCOOH
83
86
80
NR
20
DMSO
THF
37
MeOH
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
ACN
DMF
NR
45
Pip
67
K2CO3
NEt3
NEt3
NEt3
DIEPA
DIBCO
NEt3
NEt3
12
75
60
Pd (PPh3)4
PdO@TTAS
PdO@TTAS
PdO@TTAS
PdO@TTAS
68
64
40
55
12
aReaction conditions: Aryl halide (1 mmol), HCOOH (3 mmol), EDC.HCl (2 mmol), DMF(2 ml), PdO@TTAS (15 mg), 80 °C, triethylamine (1.2 mmol), 3 h,
Isolated yield based on aryl halides.
When substrates with electron‐withdrawing moieties,
such as ‐NO2, ‐COCH3, ‐F, ‐CHO and ‐CN, good to excel-
lent yields of the formylated product were obtained
(Table 2. Entries 3, 4, 6, 7 and 12). Electron‐donating
groups, such as –OMe and ‐Me gave the corresponding
products in good yield (Table 2. entries 2, 5, 9, 16). In addi-
tion, the electronic properties of ortho and meta substituted
aryl halide had little influence of products in lower yield
compared with para substituents (Table 2, entries 10 and
14), due to steric hindrance between the aryl halide and
palladium catalyst. Aryl iodides with bromo substitutions
were also tolerated well and provided target products, but
a moderate amount of yield was observed in bromo substi-
tution. Further, the NH2, OH functional groups exhibited
very less amount of yields was observed and equal amount
of N‐phenyl formate byproduct also obtained, due to dehy-
dration coupling reaction between the ‐NH2, ‐OH and
formic acid in the presence of EDC.HCl (Table 2, entries

SADHASIVAM ET AL.
11 of 17
TABLE 2 PdO@TTAS catalyzed formylation of various aryl halides with CO source HCOOH/EDC.HCla
Entry
Aryl halide
Product
Temp. (°C)
Time (h)
Yield (%)
TON
1
80
3
90
2859
2
3
80
80
3
3
80
85
2364
2304
4
80
3
86
2237
5
90
80
80
95
90
100
4
4
3
3
3
5
76
79
81
68
50
41
2095
2225
2354
1329
1142
1207
6
7
8
9b
10c
11
12
80
90
3
3
75
63
2630
2052
13
80
3
70
2656
14
15
80
90
3
4
82
67
2520
2753
16
17
80
95
3
4
78
72
1797
1144
18
80
3
78
3226
aReaction conditions: Aryl halide (1 mmol), HCOOH (3 mmol), EDC.HCl (2 mmol), DMF (2 ml), PdO@TTAS (15 mg), 80 °C, triethylamine (1.2 mmol), 3 hr,
Isolated yield based on arylhalides TON = mol products/per mol Pd,
bPhenyl formate,
cN‐phenyl formate was observed.

12 of 17
SADHASIVAM ET AL.
TABLE 3 Catalytic efficiency of the different palladium metal
products in good to excellent yields (Table 2, entries 14 and
15), Finally, the 4,4′‐diiodobiphenyl derivatives also
formylated both sides at 95 °C for about 4 h provide good
to excellent yield 72% (Table 2, entries 17).
source in the carbonylation of aryl halides reactionsa
Entry
Catalyst
Yield
1
2
3
4
5
6
Pd/C
60
72
45
54
59
90
Pd (OAc)2
Pd (PPh3)4
Pd/TATAE
Pd@TATAM
PdO@TTAS
2.3 | Reusability test
Easy to separation the desired product and reusability of
the heterogeneous catalyst are an important one for
industrial applications and an advantage of PdO@TTAS
is its reusability. The reusability of PdO@TTAS heteroge-
neous catalyst was carried out carbonylation of aryl
halide reaction in 4‐iodoanisole with HCOOH/EDC.HCl
under the optimal reaction conditions (Figure 12a). The
catalyst was recovered by normal filtration using
Whatman‐40 filter paper. The filtered residual solid cata-
lyst was washed thoroughly with methanol and water to
removed starting material and followed by vacuum
aReaction conditions: Aryl halide (1 mmol), HCOOH (3 mmol), EDC.HCl
(2 mmol), DMF (2 ml), 80 °C,triethylamine (1.2 mmol), 3 hr, Isolated yield
based on aryl halides,
bour group was previously reported palladium catalyst.
9 and 10). It is worth noting that the hetero aryl halides
such as 2‐iodothiophene, 2‐iodofurfural and 3‐
bromopyridine performed well to afford the corresponding
TABLE 4 Comparison data for pervious reported literature carbonylation of aryl halide reactions with various CO sources
S. No Catalyst
Solvent Ligand Additive
CO Source Base
Temp (°C) Time (hrs) Yield (%) Ref
Carbonylation reactions
[36]
1
2
Pd (OAc)2
Toluene X‐phos
Ac2O
DMAP
‐
HCOOH
CO gas
CHCl3
NEt3
‐
80
150
80
12
24
12
10
12
20
6
70
75
85
75
87
89
88
83
90
90
[37]
[35]
[29]
[38]
[39]
[40]
[41]
[42]
Pd (PtBu3)2 Toluene X‐phos
3
Pd (OAc)2
Pd (OAc)2
Pd (OAc)2
Pd (OAc)2
Pd (OAc)2
Pd (OAc)2
Pd (PtBu3)2
PdO@TTAS
Toluene DMAP
DMF PCy3
Toluene X‐phos
KOH
NEt3
NEt3
4
DCC
Ac2O
DPPP
DCC
KF
HCOOH
HCOOH
CO gas
HCOOH
NFS
80
5
80
6
DMSO
Toluene
DMF
‐
60
7
PCy3
‐
150
80
8
X‐phos
NEt3
NEtPr
NEt3
20
24
3
9
ACN
‐
‐
‐
CO gas
HCOOH
115
80
10
DMF
EDC. HCl
Present work
FIGURE 12 (a) Reusability experiment of PdO@TTAS catalyst; (b) Effect of reaction time and the percentage of iodo benzene conversion
in PdO@TATAs catalyzed carbonylation reactions and Hot filtration test for PdO@TATAS catalyst

SADHASIVAM ET AL.
13 of 17
SCHEME 3 Synthesis of substituted aldehyde from carbonylation of aryl halide reactions
drying at 85 °C for 1 hr. Further, the catalyst was reused
with a fresh charge of solvent and reactants for the next
four sequential recoveries; the minor loss of product yield
was steadily decreased after each cycle, in addition to
that, the FT‐IR and UV‐diffused reflectance spectra of
reused catalyst didn't show any changes in the stretching
bands and absorbance bands compared with fresh
PdO@TTAS catalyst. These data clearly speculated that
catalyst was well maintained and its structural regularity
did n't show any changes during the course of the reac-
tions (See SI Figure S1 and S2), these results indicating
that stability and reusability of the PdO@TTAS heteroge-
neous catalyst.
carbonylation of arylhalides, 4‐iodoanisole as a model
substrate. As a Figure 12b shows, when the catalyst was
separated from reaction mixture after one and half hour
by centrifugation under hot condition, the filtered portion
was added to the another reaction vessel and stirred for
further one and half hours under same optimized condi-
tions, the conversion of the filtered sample (catalyst fil-
tered) remains practically unchanged, while the
unfiltered one that the present in heterogeneous catalyst
to increase product conversion. However, Figure 12b also
shows that once the reaction solution is filtered, the
obtained solution shows there is no significant improve-
ment in the product conversion. These results proved that
the PdO@TTAS were stable at the reaction condition and
no leaching of PdO NPs in the filtrate solution, it's con-
firmed that the catalyst is truly heterogeneous in nature.
2.4 | Hot filtration test
Finally, the leaching experiment of PdO@TTAS heteroge-
neous catalyst was investigated by hot filtration test for
2.5 | Proposed mechanism
In order to investigate, the plausible mechanism for
carbonylation of arylhalide catalyzed by PdO@TTAS het-
erogeneous catalyst was proposed in Scheme 3, which
consisted with previous reported literature.[34,38] In the
first step the oxidative addition of aryl halide interact with
palladium nanoparticles to form the Pd complex II and
then followed by insertion of carbon monoxide from in‐situ
SCHEME
arylhalides catalyzed by PdO@TTAS
4
Plausible mechanism for carbonylation of

14 of 17
SADHASIVAM ET AL.
generated HCOOH/EDC.HCl in the presence of
triethylamine to generate in‐situ CO gas.
reflectance spectra was recorded using JASCO‐500. 13C
CP‐MAS NMR was recorded using a Bruker Avance
500 MHz operating at 75 MHz for 13C nuclei. The FT‐IR
spectra were recorded from a JASCO FT/IR‐410 spec-
trometer. The thermal stability of the samples was evalu-
ated by TGA (SCINCO thermal gravimeter S‐1000, Japan)
under the Argon (Ar) atmosphere over the temperature
range up to 30–800 °C, in flowing argon gas at the heating
rate of 10 °C min−1. The surface area of the samples was
calculated by using the Brunauer–Emmett–Teller (BET)
method and the pore sizes of the samples were calculated
using the NL‐DFT model. Powder X‐ray diffraction
(PXRD) patterns were obtained on a Rigaku diffractome-
ter using CuKα (λ =1.5404 Å) source with a scan rate of
0.5o min−1. The N2 adsorption–desorption isotherms were
measured on a BELsorp‐Max (BEL, Japan) at 77 K. The
morphology and particle size of the polymerized mate-
rials were examined by SEM and TEM. The scanning
electron microscopy (SEM) measurements were per-
formed by VEGA3 TESCAN, Czech Republic. The Energy
dispersive X‐ray spectroscopy (EDX) was carried out
using Bruker Nano, Germany. Silica gel‐G plates (Merck)
were used for TLC analysis with a mixture of n‐hexanes
and ethyl acetate as an eluent. Column chromatography
was carried out on silica gel (60–120 mesh) using n‐
hexanes and ethyl acetate as an eluent.
After that, CO gas interact with metal to form M‐π
interaction (complex III), and then followed by CO
migration occurred (complex IV), next step formic acid
coordinated to the η3‐bonding mono dentate ligand (com-
plex V) and followed by decarboxylation, the reductive
elimination reaction was occurred to obtain expected
desired product. Further, the catalyst PdO@TTAS was
successfully continued to further consecutive cycles. Fur-
thermore, from the comparison data for pervious
reported literature carbonylation of aryl halide reactions
with various CO sources and different palladium catalyst,
ligands, additives are summarized in Table 4.
3 | CONCLUSIONS
In conclusion, we have designed, synthesis of PdO NPs
supported on triazole functionalized triazine containing
covalent organic polymer (PdO@TTAS). The catalytic
activity of PdO@TTAS to carry out the carbonylation of
aryl halides with formic acid as a CO source, highly desir-
able, environmentally acceptable reagents, economically
viable and hazardous free, although it has to activate by
a sacrificial material, such as EDC.HCl. In addition, the
reaction was carried out without any additional stabiliz-
ing agents such as ligands, additives and also we got very
good to excellent yield over a very short reaction time.
The reaction system shows tolerance toward numerous
substituted aryl halide to obtain the desired products in
good yield, there is no reports describing to generate CO
gas with the help of HCOOH/EDC. HCl into the carbon-
ylation of aryl halides. Furthermore, the catalyst
PdO@TTAS represents a very good reusability results,
and without significant loss of the catalytic activity also
observed after five sequential runs. Hence, the reactions
employing environmentally friendly solvent and no
additives/inert atmosphere/ligand free protocol.
4.2 | Synthesis of 4,4′,4″‐(1,3,5‐triazine‐
2,4,6‐triyl)trianiline
To a stirred solution of 4‐aminobenzonitrile (2 g, 16.
92 mmol) was dissolved in a very less amount of CHCl3
under a nitrogen atmosphere and maintained at 0 °C for
about 1 hr. After that trifluoromethanesulfonic acid
(CF3SO3H) (4 ml) was drop wisely added into the
reaction mixture and stirred well, further the reaction
mixture was warmed to room temperature and stirred
for 8 hr. The resultant light yellow pasty solid was
obtained and then crushed ice added into the pasty
solid, neutralized with ammonium hydroxide to get a
desired light yellow precipitate. Further, the insoluble
precipitate was filtered off and washed with water, and
then yellow colour powder was dried in vacuum oven
at 60 °C to afford 80% of pure product (see SI Figure
12 & 13).
4 | EXPERIMENTAL SECTIONS
4.1 | Materials and methods
All the chemicals and reagents were purchased from
commercial reagent suppliers, used without further puri-
fication as commercially available unless otherwise
noted. All the solvents were obtained from laboratory
reagent grade. The 1H and 13C NMR spectra were
recorded on a Bruker (Avance) 300 and 400 MHz NMR
instrument using TMS as an internal standard and CDCl3
as a solvent. Chemical shifts are given in ppm (δ‐scale)
and the coupling constants are given in Hz. UV‐Diffused
4.3 | Synthesis of TTA polymer
Compound
4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline
(0.65 g, 1.833 mmol) and formaldehyde (40% solution)
(0.165 mg, 1.833 mmol) were mixed with polyethylene
glycol (PEG‐400)/DMF(1:1) solvent taken in a 100 ml

SADHASIVAM ET AL.
15 of 17
Schlenk tube. The resultant homogeneous solution was
treated with a 6 M acetic acid drop wisely added into
the reaction mixture and then pH of the solution was
adjusted to 10 via added for 1 N NaOH solution. Further,
the reaction mixture was carried out under vigorous stir-
ring at 75 °C for about 30 mins and capped tightly, a clear
solution was obtained and then Schlenk tube was fitted
into the oil bath at 140 °C for about 48 hr. After comple-
tion of the reaction, the highly viscous liquid was poured
into 100 ml of water and stirred for 2 hr, the light yellow
colour solid was completely settled into the bottom of
aqueous solution. After that, the solid was filtered and
subsequently washed with organic solvents to remove
the unreacted starting materials. Then, the solid was
immersed in acetone for one day and filtered, dried at
80 °C under the vacuum oven for 6 hr to get 82% yield.
FT‐IR (powder cm−1) 3355, 2874, 1610, 1510, 1431,
1366, 1182, 1148, 812, 582, 529. Elemental analysis calcu-
lated from EDS analysis (Atomic %) for C 79.55, N 13.80,
O 6.59.
aq. NaoH was added drop‐wise with vigorous stirring to
adjust the pH of the precursor solution and also main-
tained constant stirring at 75 °C for about 2 hr. Finally,
the colour of the solution was changed into brownish
black and triazole functionalized palladium oxide NPs
was obtained. The solid PdO@TTAS collected and then
filtered through a Whattman 40 filter paper and washed
with MeOH (25 ml), DCM (20 ml), acetone (20 ml) and
THF (10 ml) to remove the unreacted palladium chlo-
ride, then PdO@TTAS heterogeneous catalyst was fil-
tered and dried in a vacuum oven at 70 °C for about
8 hr to obtain PdO@TTAS as a brown colored powder
(0.48 g, 87% of yield) (Scheme 2). FT‐IR (powder cm−1
)
3329, 2867, 2209, 1602, 1498, 1366, 1254, 1182, 1135,
1089, 938, 812, 582, 522. Elemental analysis calculated
from SEM‐energy dispersive X‐ray spectrascopy analysis
(Atomic %) for C 67.39, N 21.67, O 9.24, Pd 1.70. The
Pd content 1.82% were calculated from inductively
coupled plasma‐optical emission spectroscopy (ICP‐
OES).
4.4 | Synthesis of Triazole functionalized
TTAS polymer
4.6 | General reaction procedure for
carbonylation of aryl halides
The TAS solid supports (1 g, 2.821 mmol) and 3‐
bromoprop‐1‐yne (1.06 g, 8.910 mmol) was taken in a
100 ml flask and then mixed with DMF/PEG‐400 solvent
in the presence of triethylamine base (0.856 g,
8.456 mmol), then the reaction mixture was carried out
under vigorous stirring at 90 °C for about 3 hr, after that
sodium azide (NaN3) (0.55 g, 8.46 mmol) was added into
the reaction mixture and stirred at 120 °C for about 8 hr.
The resultant slurry solution was poured into the water
and neutralized with dil. HCl to obtain light brown col-
our solid. Furthermore, the solid was filtered and subse-
quently washed with organic solvents to remove the
unreacted starting materials. After that, the solid was
immersed in acetone for one day and filtered, dried at
80 °C under the vacuum oven for about 6 hr to get 80%
of yield. FT‐IR (powder cm−1) 3349, 2861, 2017, 1669,
1602, 1504, 1431, 1372, 1174, 1142, 80, 588, 516. Elemen-
tal analysis calculated from EDS analysis (Atomic %) for
C 69.70, N 18.28, O 12.02.
The potential catalytic activities of newly synthesized
and
thoroughly
characterized
heterogeneous
PdO@TTAS catalyst were analyzed by carbonylation of
aryl halide reactions. Aryl halides and HCOOH were
dissolved in DMF solvent and stirred in a closed
Schlenk tube, subsequently added PdO@TTAS catalyst
(10 mg) and followed by the addition of EDC.HCl (N‐
(3‐Dimethylaminopropyl)‐N′‐ethylcarbodiimide hydro-
chloride) and triethylamine to obtain brisk effervescence
was observed, bubbles of carbon monoxide gas are in‐
situ generated vigorously and the reaction mixture was
stirred at 80 °C for about 3 hr. After completion of reac-
tion (monitored by TLC), the mixture was neutralized
with dilute NaHCO3 solution and diluted with 5 ml
ethyl acetate, then the catalyst was removed by simple
filtration using Whatman‐40 filter paper. The filtrate
was extracted with excess amount of ethyl acetate, and
then concentrated under reduced pressure. The crude
product was further purified by column chromatography
(petroleum ether/ethyl acetate) to afford the correspond-
ing product (Scheme 4).
4.5 | Synthesis of Pd@TTAS polymer
To take a PdCl2 (0.05 g) solid metal salt and (0.5 g) of
TTAS solid polymeric supports were mixed with 5 ml
of MeOH into a 25 ml round bottom flask, the mixture
was stirred at room temperature. After that, the concen-
trated 0.5 ml of hydrochloric acid was added; the PdCl2
was converted into H2PdCl4.H2O and then subsequently
ACKNOWLEDGEMENTS
AS and VS acknowledge the financial support of the
Department of Science and Technology, SERB,
Extramural Major Research Project (Grant No.
EMR/2015/000969), Council of Scientific and Industrial

16 of 17
SADHASIVAM ET AL.
[21] F. Yang, C. Chi, S. Dong, C. Wang, X. Jia, L. Ren, Y. Zhang, L.
Research (CSIR), HRDG, ACK No: 124065/2 k17/1,
09/201(0420)/18‐EMR‐I, New Delhi, Council of Scien-
tific and Industrial Research (CSIR), HRDG, File No.
01(2901)/17/EMR‐II, New Delhi, Department of Science
and Technology DST/TM/CERI/C130(G), New Delhi,
India. Further, VS acknowledge to the financial support
of the CSIR, New Delhi for providing SRF No.
09/201(0420)18‐EMR‐I. In addition to that the authors
thanks to DST‐FIST, PURSE, UPE for providing instru-
mental facilities.
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[54] R. J. Kalbasi, N. Mesgarsaravi, R. Gharibi, Appl Organometal
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How to cite this article: Sadhasivam V,
Balasaravanan R, Siva A. PdO nanoparticles
supported on triazole functionalized porous triazine
polymer as an efficient heterogeneous catalyst for
carbonylation of aryl halides. Appl Organometal
Chem. 2019;e4994. https://doi.org/10.1002/aoc.4994
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.