Catalytic and antibacterial properties of 3-dentate carboxamide Pd/Pt complexes obtained via a benign route

Article abstract of DOI:10.1002/aoc.5531

The complexes Pd^II(qcq)(OAc) and Pt^II(qcq)Cl have been synthesized using environmentally benign synthesized ligands and characterized by elemental analyses: Fourier transform infrared spectroscopy, UV–visible spectroscopy, ¹H NMR spectroscopy, and X-ray diffraction. The catalytic activity of the complex was assessed, in different media, for the Mizoroki–Heck coupling reaction for typical aryl halides and terminal olefins under aerobic conditions. Since the base and the solvent were found to influence the efficiency of the reaction, reaction conditions, temperature, time, and the amount of K₃PO₄ and a mixture of H₂O/PEG, were optimized. We found, for the Mizoroki–Heck reaction coupling less reactive aryl chloride derivatives with olefins, promising activity for palladium catalysts. The electrochemical behavior of Hqcq and the Pd(II) complex was investigated by cyclic voltammetry and irreversible Pd^II/I reductions were observed. Hqcq and the Pd(II) and Pt(II) complexes were also screened for their in vitro antibacterial activity. They showed promising antibacterial activity comparable to that of the antibiotic penicillin.

Full text of DOI:10.1002/aoc.5531

Received: 31 October 2019
DOI: 10.1002/aoc.5531
Revised: 21 December 2019
Accepted: 8 January 2020
F U L L P A P E R
Catalytic and antibacterial properties of 3-dentate
carboxamide Pd/Pt complexes obtained via a benign route
Mahsa Kiani1 | Mojtaba Bagherzadeh1
| Soraya Meghdadi2
|
Farzaneh Fadaei-Tirani3 | Kurt Schenk-Joß4 | Navid Rabiee1
1Department of Chemistry, Sharif
The complexes PdII(qcq)(OAc) and PtII(qcq)Cl have been synthesized using
environmentally benign synthesized ligands and characterized by elemental
analyses: Fourier transform infrared spectroscopy, UV–visible spectroscopy,
1H NMR spectroscopy, and X-ray diffraction. The catalytic activity of the com-
plex was assessed, in different media, for the Mizoroki–Heck coupling reaction
for typical aryl halides and terminal olefins under aerobic conditions. Since
the base and the solvent were found to influence the efficiency of the reaction,
reaction conditions, temperature, time, and the amount of K3PO4 and a mix-
ture of H2O/PEG, were optimized. We found, for the Mizoroki–Heck reaction
coupling less reactive aryl chloride derivatives with olefins, promising activity
for palladium catalysts. The electrochemical behavior of Hqcq and the
Pd(II) complex was investigated by cyclic voltammetry and irreversible PdII/I
reductions were observed. Hqcq and the Pd(II) and Pt(II) complexes were also
screened for their in vitro antibacterial activity. They showed promising
antibacterial activity comparable to that of the antibiotic penicillin.
University of Technology, Tehran,
11155-3516, Iran
2Department of Chemistry, Isfahan
University of Technology, Isfahan,
84156-83111, Iran
3École Polytechnique Fédérale de
Lausanne, Institute of Chemical Sciences
and Engineering, CH-1015 Lausanne,
Switzerland
4Institute of Physics, École Polytechnique
Fédérale de Lausanne, CH-1015
Lausanne, Switzerland
Correspondence
Mojtaba Bagherzadeh, Department of
Chemistry, Sharif University of
Technology, Tehran 11155-3516. Iran.
Email: bagherzadeh@sharif.ed
Funding information
Sharif University of Technology, Grant/
Award Number: 1
K E Y W O R D S
carboxamide complexes, cyclic voltammetry and antibacterial activity, Pd(II) complexes, X-ray
crystal structure, Mizoroki–Heck coupling reaction
1 | INTRODUCTION
Various reactions for forming a C–C bond are cur-
rently under study because of their significant
In the last decade, numerous attempts have been made
to find green and reproducible ways of synthesizing
organic and inorganic compounds.[1] Affordability of the
synthesis procedure is considered to be the critical factor
when for use industrial applications, and in this phase,
the major barrier is certainly the use of organic and toxic
solvents. One of the most important tenets of green
chemistry lies in its use of nontoxic solvents that are
capable of increasing efficiency as well as reducing the
reaction rate. Clearly, the use of a green solvent and
finding the optimized conditions are necessary steps in
the chemistry of catalytic applications, and lead to
increased yields.[2–4]
applications.[5–7] Among them, the Mizoroki–Heck reac-
tion is, perhaps, the most strategic process for the
arylation of olefins through palladium-catalyzed C–C for-
mation reactions.[8–12] Although numerous attempts at
designing a green,[13,14] simple, cost-effective, and effi-
cient approach for this reaction have been made, there is
still ample scope for improvement. In particular, design-
ing and implementing a simple procedure based on a
fully green solvent could bring a breakthrough.[15–19]
Palladium(II) complexes have been the subject of
extensive investigation because of the structural analogy
between PtII and PdII complexes. Therefore, efforts have
recently been made to design novel anticancer drugs
Appl Organometal Chem. 2020;e5531.
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https://doi.org/10.1002/aoc.5531

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KIANI ET AL.
based on palladium compounds.[20–22] In addition, these
compounds have attracted renewed interest due to their
wide applications in catalytic processes,[23–25] construc-
tion of chemical sensors,[26] and antibacterial and cyto-
toxicity usage.[27]
used as received from Fluka and Merck, Germany,
without further purification. Elemental analysis was
performed with a Carlo ERBA Model EA 1108 elemen-
tal analyzer. FT-IR spectra were recorded from KBr pel-
lets in the window of 4000–400 cm–1 with a Unicam
Matson 1000 FT-IR spectrophotometer at room temper-
ature. UV–Vis analyses were performed on a CARY
100 Bio VARIAN spectrophotometer using quartz cells
with a 1.0 cm path length. The 1H NMR spectra of
Hqcq in dimethyl sulfoxide-d6 (DMSO-d6) were
obtained using a Bruker FT-NMR 500 MHZ spectrome-
ter; proton chemical shifts are reported in parts per mil-
lion (ppm) relative to an internal standard of Me4Si.
Gas chromatographic (GC) analyses were performed on
an Agilent Technologies 6890 N, equipped with a
19019 J-413 HP-5, 5% phenyl methyl siloxane, and a
capillary column (60.0 m × 250 μm × 1.00 μm). Cyclic
voltammograms (CVs) were recorded by using a SAMA
500 Research Analyser using a three-electrode system, a
glassy carbon working electrode (Metrohm 6.1204.110
with 2.0 0.1 mm diameter), a platinum disk auxiliary
electrode, and Ag wire as reference electrode. The
glassy carbon-working electrode was manually cleaned
with 1 μm alumina polish prior to each scan. CV mea-
surements were performed in Dimethylformamide
(DMF) with tetrabutylammonium hexafluorophosphate
(TBAH) as supporting electrolyte. The solutions were
deoxygenated by purging with Ar for 5 min. All electro-
chemical potentials were calibrated versus the internal
Fc+/0 (E0 = 0.45 V vs. Saturated calomel electrode
(SCE)) couple under the same conditions.
Based on the literature, a great number of recent pub-
lications have focused on finding suitable alternatives for
hazardous solvents, and ionic liquids (ILs) have emerged
as appropriate candidates for use in sustainable chemis-
try.[28,29] Tetrabutylammonium bromide (TBAB) has
been proven to be safe and clean in numerous studies
and to be a suitable catalyst for this type of reaction.[30–33]
Carboxamide-based compounds have been used in
several fields due to their potential applications in bio-
medical science,[34,35] catalytic processes,[36,37] and
sensors.[38–40] These compounds are based on the carbox-
amide linkage, –C(O)NH–, considered one of the most
vital and essential functional groups in nature; it also
plays an important role in bio-inspired studies.[41–43]
Extensive studies are being devoted to engineering non-
toxic carboxamide ligands for catalytic and biomedical
applications.[44–47] Catalytic applications of this type of
ligand are being considered as a promising way to opti-
mized the reactions at the bench scale and then scale
them up to the industrial phase of some crucial mecha-
nisms. To achieve this goal, the design and synthesis of
organometallic complexes from these ligands seems to be
a promising route.[48–50]
In this study, we synthesized the three-dentate car-
boxamide ligand 8-(2-quinoline carboxamide)quinoline
(Hqcq) based on the protocols mentioned in the litera-
ture, by using ILs.[51] Hqcq was incorporated in the pal-
ladium complex PdII(qcq)(OAc), which was evaluated
in the typical Mizoroki–Heck catalytic reaction. The
ligand and complexes were characterized by CHN anal-
ysis, Fourier transform infrared (FT-IR) spectroscopy,
UV–visible (UV–Vis) spectroscopy, nuclear magnetic
resonance (1H NMR) spectroscopy, single crystal X-ray
diffraction, and cyclic voltammetry (CV). This
Pd(II) complex was applied to the Mizoroki–Heck cata-
lytic reaction using polyethylene glycol (PEG) beside a
green solvent; the yield was increased and the time of
the reaction was reduced. The ligand and complexes
were also investigated in terms of their antibacterial
activity.
3 | SYNTHESIS OF THE
COMPOUNDS
3.1 | The complexes [Pdп(qcq)(OAc)]
(1) and [PdII(qcq)(OAc)].CHCl3 (1C)
First, 0.0056 g (0.0250 mmol) of palladium acetate was
dissolved in 25 ml of chloroform and added dropwise to a
solution of 0.0074 g (0.0250 mmol) of L in 25 ml of chlo-
roform. Then, 2.5 ml of DMSO was added to the solution,
which was then stirred for 4 hr after it had turned yellow.
Afterwards, the final solution was filtered and the pow-
der was left to crystallize in a refrigerator (5ꢀC) for
20 days. At this stage, some of the orange crystals grown
from the filtrate were separated and dried; single crystal
X-ray diffraction revealed these to be 1 (Scheme 1). Some
other of these crystals were, however, left in the mother
liquor, and sent to the X-ray laboratory within the
mother liquor and shown to be 1C.
2 | EXPERIMENTAL
2.1 | Materials and methods
All the reactions were carried out in air. All solvents
and chemicals were of commercial reagent grade and

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
3 of 18
239(50290). 1H NMR (400 MHz, (CD3)2SO) δ (ppm):
7.630–9.730 (12ArH).
3.3 | Data collection, determination, and
refinement of the structures
SCHEME 1 Schematic representation of complexes 1 and 2
3.3.1 | Growth
C21H15N3O3Pd (463.76 g/mol–1 ): yield 90%; anal.
calc: C 54.38, H 3.26, N 9.06; found: C 53.45, H 3.188, N
8.976%. FT-IR (KBr, cm–1 ) νmax: 1638 (s, C=Oamidic),
1594 (s, C=Ocoord.OAc), 1395 (s, C=Ocoord.OAc). UV–Vis
(DMF) λmax (nm) (ε, L mol–1 cm–1): 446 (3070),
Pale-yellow crystals of L suitable for X-ray diffraction
were obtained by slow evaporation of a solution of 2Y in
acetone–water (30:2 v/v) and orange crystals of 1 and 1C
suitable for X-ray diffraction were obtained by slow evap-
oration of a solution in chloroform–DMSO (10:1 v/v) at
refrigerator temperature.
1
398 (9806), 354 (8922), 292(18442). H NMR (400 MHz,
(CD3)2SO) δ (ppm): 7.667–8.845 (12ArH), 2.001 (s, 3H,
CH3COO).
3.3.2 | Data collection of L and 1
3.2 | The complex [Ptп(qcq)cl] (2)
Bragg intensities of L and 1 were collected at the Swiss-
Norwegian Beam-Line at the ESRF, Grenoble, France. A
wavelength of 0.6957 was selected using a Si (111) double
crystal monochromator. A combination of curved mirrors
and monochromators produced a focused beam at the
position of the crystal. The crystals of L and 1 were
maintained at temperatures of 120 (2) and 100 (2) K using
an N2 Cryostream, respectively. The intensities were
collected by means of a Pilatus2M pixel detector from
Dectris Ltd, Switzerland). Cell refinement, data reduc-
tion, and absorption correction were carried out with
CrysAlisPro.[52]
First, 0.0103 g (0.0250 mmol) of potassium tetrachlo-
ropalatinate was dissolved in 2 ml of water and added
dropwise to a solution of 0.0074 g (0.0250 mmol) of
L in 30 ml of acetone. After the solution had turned
bright pink, it was refluxed for 2 hr. After 2 hr, the pale
yellow solution was filtered and the powder placed in a
refrigerator (5ꢀC) to form crystals for 5 days. Two types
of crystals formed in this way; they were separated with
the help of a Büchner funnel and 20 ml acetone. The
bright orange crystals dissolved in acetone and were
thus removed, whereas the red crystals remained in
acetone.
Then, 1 ml of water was added to the bright orange
solution and the mixture placed in a refrigerator. After
3 days, pale yellow crystals of 2Y were obtained. After
examining their spectra, it became clear that these
crystals corresponded to the additional ligand that co-
crystallized with the platinum complexes. The final
pale-yellow crystals obtained from the solution were
investigated by single crystal X-ray diffraction at the
European Synchrotron Radiation Facility (ESRF).
The red product was dissolved in 20 ml of acetoni-
trile, then the solution was filtered and placed in a sta-
3.3.3 | Data collection of 1C
Bragg intensities of 1C were collected, at room tempera-
ture, on a Stoe IPDS II using graphite-monochromatized
MoKα (λ = 0.71073 Å) with the help of X-Area
WinXpose.[53] The cell refinement was carried out by
means of X-Area Recipe,[54] data reduction, and a numer-
ical absorption correction, based on the habitus, with
X-Red32[55] and X-Area Integrate.[56]
The solutions and refinements of the structures were
performed by the latest available versions of ShelXT[57]
and ShelXL.[58] All non-hydrogen atoms were refined
anisotropically using full-matrix least-squares based on|
F|2. The hydrogen atoms were placed at calculated posi-
tions by means of the “riding” model in which each
hydrogen atom was assigned a fixed isotropic displace-
ment parameter with a value equal to 1.2 Ueq of its parent
carbon atom (1.5 Ueq for the methyl groups). Details of
the data collection, structure solution, and refinement of
L, 1, and 1C are compiled in Table 1.
tionary position on the table to obtain
a slow
evaporation after 5 days of red crystals (2R), which
were not suitable for crystallography of X-ray diffraction
(Scheme 1).
C19H12ClN3OPt (528.85 g/mol): yield 60%; anal. calc:
C 43.15, H 2.29, N 7.95; found: C 43.74, H 2.19, N 7.989%.
FT-IR (KBr, cm–1) νmax: 1639 (s, C=Oamidic), 1575 (s,
C–N). UV–Vis (DMF) λmax (nm) (ε, L mol–1 cm–1):
620 (230), 660(90), 377 (74200), 361 (79200), 280(23720),

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KIANI ET AL.
TABLE 1 Data collection, structure solution, and refinement for L/2R, 1, and 1C
Compound
Formula
Dcalc. (g/cm–3
L/2R
1
1C
C19H13N3OPt
1.399
C21H15N3O3Pd
1.803
C22H16Cl3N3O3Pd
1.844
)
μ (mm−1
)
0.134
0.977
1.297
Formula weight
Color
300.29
Yellow
Prism
463.76
583.13
Orange
Orange
Shape
Plate
Plate
Size (mm3)
0.23 × 0.12 × 0.09
120 (2)
Orthorhombic
0.31 (3)
Pna21
0.19 × 0.09 × 0.07
100 (2)
0.65 × 0.04 × 0.03
298 (2)
T (K)
Crystal system
Flack parameter
Space group
a (Å)
Orthorhombic
Monoclinic
Pbcn
P21/n
8.6455 (2)
20.0526 (2)
12.3275 (2)
90
9.9727 (2)
30.3854 (8)
4.7050 (3)
90
8.2989 (4)
17.8178 (8)
23.1105 (7)
90
b (Å)
c (Å)
α (ꢀ)
β (ꢀ)
γ (ꢀ)
90
90
100.563 (2)
90
90
90
V (Å3)
1425.73 (10)
4
3417.3 (2)
8
2100.94 (6)
4
Z
Z'
1
1
1
Wavelength (Å)
Radiation type
Θmin (ꢀ)
0.6957
Synchrotron
2.104
0.69563
Synchrotron
2.237
0.71073
MoKα
1.964
Θmax (ꢀ)
24.457
15276
25.768
16678
3430
26.989
9306
Measured reflection
Independent reflection
Reflections with I > 2 (I)
Rint
2031
2822
2001
3188
2636
0.0359
219
0.0466
254
0.0436
496
Parameters
Restraints
Largest peak (e/Å3)
Deepest hole (e/Å3)
GooF
1
0
923
0.173
3.448
0.408
−0.122
1.043
−1.803
1.094
−0.494
1.083
wR2 (all data)
wR2
0.0708
0.0707
0.0269
0.0267
0.1651
0.1628
0.0645
0.0616
0.0760
0.0737
0.0295
0.0271
R1 (all data)
R1
P
P
P
P
R1 = ||Fo| – |Fc||/ |Fo|, wR2 = [ [w(Fo2 – Fc2)2]/ [w(Fo2)2]]1/2
The entire complex 1C is disordered over two posi-
tions (Figure 3), which could be located in a difference
map and refined anisotropically, yielding site occupancy
ratios of 0.803 (2)/0.197 (2), but SADI restraints were
used to optimize the bond lengths and SIMU restraints
were applied to refine the displacement ellipsoids of the

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
5 of 18
atoms. Aromatic groups were restrained to have an ideal
hexagonal geometry using the card AFIX 66.
There seems to be a second, disordered complex in
structure 1 (much as in the chloroformate 1C), but it was
impossible to refine it.
at 500 μg/ml was recorded. Stock solutions of compounds
were prepared in DMSO. The MZI produced by the
compounds were compared with the standard antibiotic
penicillin of similar concentration. Each test was carried
out three times to minimize the error. In order to clarify
any effect of DMSO in the biological screening, blank
studies were carried out, and no activity was observed
against any bacterial strains in pure DMSO.
3.4 | General procedure for catalytic
reaction
All Heck reactions were carried out in air. A mixture of
aryl halide (1.0 mmol), olefins (1.2 mmol), K3PO4
(2 mmol), and [PdII(qcq)(OAc)] (0.5 mol%) in a 2:1 mix-
ture of H2O/Polyethylene glycol (PEG) (3 ml) was
allowed to react in a sealed tube at 130ꢀC and comple-
tion of the reaction was judged by thin layer chroma-
tography (TLC). Then, H2O (5 ml) was added to the
resulting mixture and the product was extracted with
diethylether (3 × 10 ml) from the aqueous phase. The
aqueous solution was separated from the organic layer,
which was dried with anhydrous CaCl2. The solvent
was removed under reduced pressure to give the desired
product. To obtain the pure products, after extraction
with ethyl acetate, the reaction mixture was filtered and
the residue was subjected to column chromatography
using ethyl acetate/n-hexane (1:3).
4 | RESULTS AND DISCUSSION
4.1 | Synthesis and characterization
4.1.1 | Synthesis of the Pd complex
Equimolar quantities of palladium acetate and the ligand
L were used for the synthesis of the Pd(II) complex of
the three-dentate carboxamide ligand. Orange crystals of
1 grew by slow evaporation of a solution in chloroform–
DMSO (10:1 v/v) after 20 days at refrigerator-
temperature (5ꢀC).
4.1.2 | Synthesis of the Pt complex
Equimolar quantities of potassium tetrachloroplatinate
and the ligand L were used for the synthesis of the
Pt(II) complex of the three-dentate carboxamide ligand.
Dark-red crystals (2) and pale-yellow crystals (L) grew by
slow evaporation of a solution in H2O–acetone after
5 days at refrigerator temperature (5ꢀC).
3.5 | Biological studies
The ligand and the Pd(II) and Pt(II) complexes were
individually tested against a panel of microorganisms
(Gram-negative and Gram-positive), namely Bacillus
cereus and Staphylococcus aureus (Gram-positive) and
Salmonella, Klebsiellap neumoniae, and Escherichia coli
(Gram-negative) species. The organisms were grown by
the well-known diffusion method using Sabouraud
dextrose agar and Müller Hinton agar. The minimum
zone of inhibition (MZI) was recorded on completion of
the incubation and the mean diameter for each complex
4.1.3 | Discussion of the structures
The structures of L/2R, 1, and 1C with their atom num-
bering scheme are presented in Figures 1–3 and selected
bond angles and distances are listed in Table 2.
FIGURE 1 The structure of L/2R.
Displacement ellipsoids are drawn at the 50%
probability level

6 of 18
KIANI ET AL.
With hindsight, these results become very clear.
Visual inspection of the grown crystals of 2 showed two
different habits/aspects: (a) yellow crystals with red spots
and (b) dark-red crystals. Both grew dendrite-like and
were of low quality, but at the synchrotron it was never-
theless possible to chip off a part of the entangled crystal
mass and obtain a good diffraction pattern.
Despite the absence of an asymmetric atom, L' crys-
tallizes in the SOHNCKE group P212121. The structure of
L' consists of isolated [100] stacks of L molecules that
can be imagined as parallel horseshoes. Their ends
(i.e., the quinoline moieties) are slightly twisted (11.54
(3)ꢀ). There are four such stacks per cell, each of which is
generated by the action of a two-fold screw rotation of
the space group. There are three intramolecular N–Hꢁ ꢁ ꢁN
and C–Hꢁ ꢁ ꢁO hydrogen bonds, but no intermolecular
ones. The structure owes its cohesion to π–π interactions
(centroid–centroid 3.7351 (14) Å) and dispersion forces
(Tm = 430 K).[60] Hydrogen bonds and other interactions
for L/2R, 1, and 1C are collected in Table 3.
FIGURE 2 The structure of [PdII(qcq)(OAc)] (1).
Displacement ellipsoids are drawn at the 50% probability level
In the structure of L we still find the [001] stacks of
horseshoes, but their angle with respect to the stack axis
is different and the centroid–centrssoid distance is much
longer (~4.7 Å). The two quinoline moieties in L' subtend
an angle of 12.42ꢀ, while those in L are more parallel
(5.126ꢀ). Since we observe the same intra- and inter-
molecular hydrogen bonds, and since the π–π interac-
tions are much weaker, this seems to be a true van der
Waals structure. Since the structure of L is different to
that of L', we might think the difference is due to the
presence of Pt, but we must not be fooled into thinking
that L is the true structure of 2R. The Pt–N distances, for
example, do not seem to be justifiable. A crude minimiza-
tion indeed leads to more common values [IT, C], but
certainly the Pt coordination in this complex can be
assessed as slightly distorted square planar.
The structure of L presented here is not the result of
an intentional attempt at growing L, but rather a bizarre
outcome of a crystallization of complex 2. When first
determining its structure, only L was found, but in the
final stages we found a residuum of 0.5 eÅ−3 at the exact
position of a metal ion for structure 2, which we named
Pt. A refinement yielded site occupancy factor of 0.0051
(5) for the Pt atom and the R1 value decreased from 0.032
to 0.0267, but it was impossible to locate the chlorine
atom in difference maps. Since our structure of L is dif-
ferent to that already reported,[59] and named L'
(an overlay of L and L' is shown in Figure 4), we report
this surprising structure anyway, since it might inspire
some researcher when addressing similar questions and
as a fringe benefit it also furnishes a rough structure of 2.
FIGURE 3 The structure of 1C.
Displacement ellipsoids are drawn at the
50% probability level

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
7 of 18
TABLE 2 Relevant bond lengths (Å) and other items for L/2R, 1, and 1C
1
1C
IT/C
Pd–Namide
N2, 1.933 (5)
N2, 1.960 (3)
2.037 (Schiff base)
2.089 (pyridine)
Pd–Nquinoline
N1, 2.035 (5)
N3, 1.990 (5)
N1A, 2.062 (4)
N3A, 2.022 (4)
Pd–Oacetate
Pd–Cl
O3, 2.005 (4)
–
O3A, 2.037 (4)
–
2.115–2.164
–
∠
quinoline (ꢀ)
9.725
5.095
SSE (Å2)
0.00184
L/2R
0.0055
Relaxeda
2.027
IT/C
Pt–Namide
N2, 1.898 (18)
1.995–2.175
2.085
Pt–Nquinoline
N1, 2.01 (2)
N3, 2.29 (2)
2.125
2.115
Pt–Oacetate
Pt–Cl
–
–
–
n/a
Cl1, 2.409
2.319
∠
quinoline (ꢀ)
SSE (Å2)
6.293
0.00441
aUsing the relax option in CrystalMaker. Minimised energy.
Abbreviations: ∠quinoline, angle of quinolone; IT/C, International Table for Crystallography volume C; SSE, sum of squared errors.
FIGURE 4 Overlay of the two ligands
L0 and L
Since acetone is a weakly coordinating solvent, we
can surmise that 2R exists in solution as such. 2R is pre-
sent in the mother liquor, since it is slightly soluble in
the washing liquid (acetone). Comparing the structures
of L, 1, and 1C, we understand that the factor determin-
ing these structures is more or less slanted stacks of
horseshoes. According to Ostwald's Rule of Stages, it
would be L to nucleate first, then 2R. At the end of the
process, L would transform into 2R, but since very little
Pt is available, we would obtain little (red) islands of 2R
bridged by bigger yellow regions of L" (meaning a dis-
torted version of L). In fact, the extension of a cluster of
2R should not be feasible because of lack of Pt, but it
seems so favorable to dock the ligand L without the
metal that we observe the growth of a distorted structure.
The positive point is that we thus obtain a rough struc-
ture of 2R. This might be another example of interlaced
crystals,[61] but this assertion would need experimental
confirmation.
In addition, the L' morphology has been investigated
via field emission scanning electron microscopy (FE-
SEM) and energy dispersive X-ray spectroscopy (EDS)
analysis (Figure 5). These analyses proved the presence
of Pt and Cl on the surface of L’, proving that the Pt com-
plex is partially crystallized on the surface. In addition,
based on the FE-SEM results, some parts of them were
covered by Pt nanometer particles. Figure 5 also shows
the weight percentages, which indicate that a small
amount of Pt complex is crystallized with L.
In addition, we obtained two types of crystals when
synthesizing the platinum complex. To prove the exis-
tence of Pt next to L in the crystallization of the platinum
complex, we carried out X-ray diffraction on the three
crystals (A, B, and C) shown in Figure 6.

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KIANI ET AL.
TABLE 3 Hydrogen bonds and other interactions for L/2R, 1, and 1C
D
–H
ꢁꢁꢁA
d(D–H) (Å)
d(HꢁꢁꢁA) (Å)
d(D–A) (Å)
D–HꢁꢁꢁA (ꢀ)
L/2R
N2
H2
H2
H5
H12
N1
0.88
0.88
0.95
0.95
2.25
2.28
2.41
2.26
2.682 (3)
2.679 (2)
3.337 (3)
2.869 (3)
110.1
108.0
165.0
121.0
N2
N3
O1k1
C5
C12
1
O1
C2
H2
O3
0.95
0.95
0.95
0.95
0.95
0.95
2.12
2.35
2.50
2.48
2.48
2.47
2.989 (7)
2.923 (7)
3.023 (7)
3.377 (8)
3.316 (8)
3.094 (6)
152.0
118.0
115.0
158.0
147.0
123.0
C12
C18
C5
H12
H18
H5
O1
O3
O2 m1
O2 m2
O1 m3
C16
C18
1C
H16
H18
C2A
C12A
C18A
C14A
C22
C2A
C17A
C5A
C13A
Cl1
H2A
O3A
0.93
0.93
0.93
0.93
0.98
0.93
0.93
0.93
0.93
2.17
2.37
2.60
2.48
2.24
2.17
2.93
3.01
3.09
3.033 (7)
2.944 (9)
3.106 (7)
3.389 (8)
3.206 (6)
3.033 (8)
3.852 (6)
3.908 (5)
3.546 (4)
3.067 (8)
154.0
120.0
115.0
164.0
168.1
153.8
172.2
163.1
111.8
H12A
H18A
H14A
H22
O1A
O3A
O1A p1
O2A
H2A
O3A
Cl1 p2
H17A
H5A
Cl1
H13A
Cl2 p3
O2A p4
k1, 1/2 + x, ½ – y, 1 + z; m1, 1 – x, 1 – y, 1 – z; m2, –x, y, 3/2 – z; m3, 1/2 – x, 1/2 + y, z; p1, –1/2 + x, 1/2 – y, 1/2 + z; p2, –1 + x, y, 1 + z; p3, 1/2 –x, –1/2 + y,
1/2 – z; p4, –1/2 + x, 1/2 – y, –1/2 + z.
FIGURE 5 FE-SEM image of L0 at (a) 1 μm and (b) 200 nm, and (c) EDS spectrum of L0
Figure 6 shows the diffraction images of the three
crystals and their determined cell parameters, which
show that the values of the a and b axes in the Pt com-
plex falls in the same range as L, Pt can be seen in the
structure of L. Comparing Figure 6c with Figure 6a and
Figure 6b shows that the ligand is crystallized by the Pt
complex.
The structure of 1 also consists of [100] stacks of
horseshoe shapes which roughly lie in the (102) plane
and of which the normal subtends an angle of 54.5ꢀ with

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
9 of 18
FIGURE 6 X-ray diffraction images of the three different crystals: (a) L, (b) 2R, and (c) L0
FIGURE 7 Overlay of the
complexes 1 and 1C
the vector c. Neighboring stacks along b have the oppo-
site tilt, but also along c. The application of {C2y|0012} gen-
erates a dimer stabilized by π–π interactions (centroid–
centroid distance 3.44 Å). The structure is further stabi-
lized by three intra- and three intermolecular hydrogen
bonds (Table 3). The entire Pd complex 1 is probably
also disordered over two orientations (as in 1C) in
which the planes of L all but coincide (overlay of 1 and
1C is shown in Figure 7). The Pd1, N1, N2, N3, and O3
atoms lie in a plane of root-mean-square deviation
(RMSD) = 0.019 Å, but the trans angles O3–Pd1–N2
and N3–Pd1–N1 of 174.0 (17)ꢀ and 164.0 (2)ꢀ indicate
that the coordination geometry around the palladium
atom is a flat, distorted square. The dihedral angle
between the N,N chelate rings Pd1–N1–C9–C10–N2 and
Pd1–N2–C11–C19–N3 is 4.50 (19)ꢀ in 1. The average
Pd–Namide bond length (1.933 (5) Å) agrees with those
reported (1.957 Å) for other deprotonated Pd–Namide
bonds and is shorter than the Pd–Nquinoline bond length
(2.012 (5) Aꢀ). This is in accord with the fact that the
deprotonated amide nitrogen is a very strong donor.[62]
Figure 7 shows an overlay of complexes 1 and 1C dem-
onstrating that there is hardly any geometrical differ-
ence in the coordination of these two complexes.
complexes are turned in opposite directions to form
dimers; the two complexes are related by an inversion
such that the quinoline moieties are superimposed
ꢀ ꢀ
approximately perpendicular to [201], providing extra sta-
bility to the structure by π…π interactions. The chloro-
form moieties roughly face the acetate groups and form
C–H…Cl hydrogen bonds, partly along the a stacks and
partly parallel to b and c, thus establishing a three-
dimensional network of hydrogen bonds. The latter is
completed by C–HꢁꢁꢁO hydrogen bonds along [101] and
ꢀ
[101 ], and there is an OꢁꢁꢁCl halogen bond as well
(Table 3 and Figure 8). Despite the high packing coeffi-
cient of 0.724 there seems to be some extra space (and
the horseshoes have almost mirror-symmetry) in the
cavity for the complex such that two orientations, related
ꢀ
by a (122) non-crystallographic mirror plane, are energet-
ically very comparable (major/minor
=
0.8031
(19):0.1969 (19)). There is an angle of 5.1ꢀ between the
quinoline moieties and the coordination sphere of Pd is
perfectly flat (0.0055Å2). With trans angles of 163.279 and
172.39ꢀ we may call the coordination distorted square-
pyramidal.
The structure of 1C also consists of [100] stacks of the
Pd complexes which lie roughly in the (101) plane and
subtend an angle of 42.7ꢀ with the (100) plane. All the
planes in the structure are parallel and their distance is
approximately 3.3 Å. The acetate groups on neighboring
4.1.4 | Spectral studies
The FT-IR spectra of L, 1, and 2R are shown in
Supporting Information Figures S1–S3. The amidic νN–H
band of L appears in the 3313 cm−1 region, but is

10 of 18
KIANI ET AL.
FIGURE 8 Stereoscopic view of the interactions in 1C
absent in the spectra of the complexes, which indicates
that L is coordinated to the metal in the deprotonated
form.[63] The carbonyl stretching frequency, νC=O, lies
at 1674 cm−1 in L, but is red-shifted to 1638 and
1639 cm−1, respectively, for the Pd and Pt complexes.
Furthermore its intensity decreases considerably after
the formation of the complex, which is a strong indica-
tion for the coordination of deprotonated complexes.[64]
νC–N appears at 1526 cm−1 in L, but at 1593 and
1575 cm−1, respectively, for the Pd and Pt complexes.
Its intensity increases significantly owing to an increase
in the resonance in the deprotonated amide of the
complexes.[63]
280 nm (ε
=
23,720
L
L
mol−1 cm−1), 361 nm
(ε 79,200
=
mol−1 cm−1), and 377 nm
(ε = 74,200 L mol−1 cm−1) may be explained as ligand
field transitions with a CT admixture. The new shoulders
for 2R at 620 nm (ε = 230 L mol−1 cm−1) and 660 nm
(ε = 90 L mol−1 cm−1) may indicate that the square-
planar structure of the complex presents a very slight
tetrahedral distortion.
1
The H NMR spectrum of L was recorded in CDCl3
solution and the corresponding data are shown in
Supporting Information Figure S7 along with the spec-
trum of L reported in the literature.[51] Its main features
are the signal due to the amidic proton N–H at
12.38 ppm. The aromatic protons of L appear in the
appropriate region (7.688–9.105 ppm).
The UV–Vis spectra of L, 1, and 2R are shown in
Supporting Information Figures S4–S6. The spectrum of
L shows a shoulder at 335 nm (ε = 14,432 L mol−1 cm−1
)
The H NMR spectra of 1 and 2R were acquired in
1
and
(ε
two
41,232
overlapping
bands
at
264
nm
DMSO-d6 solution and the corresponding data may be
found in Supporting Information Figures S8 and S9.
Their main feature is the absence of N–H signals, which
confirms that the ligand is coordinated in its
deprotonated form. The aromatic protons of these
compounds appear in the appropriate regions:
7.667–8.845 ppm for 1 and 7.630–9.730 ppm for 2R. The
signals of the methyl protons of the acetate ligand appear
at 2.001 ppm for 1.
=
L
mol−1 cm−1) and 281 nm
(ε = 32,058 L mol−1 cm−1). After the formation of the Pd
complex, the peak positions of L are red-shifted: the peak
at 264 nm (ε = 41,232 L mol−1 cm−1) to 292 nm
(ε = 18,442 L mol−1 cm−1) and the two broad bands to
354 nm (ε = 8922 L mol−1 cm−1) and 398 nm
(ε = 9806 L mol−1 cm−1). These shifts may be explained
as ligand field transitions with a Charge Transfer (CT)
admixture. The new shoulder in the spectrum of the
complex at 446 nm (ε = 3070 L mol−1 cm−1) may be
taken as an indication of a very slight distortion of the
square-planar structure of the complex.[65] But remember
the X-ray diffraction results: the coordination of the
metal is quite flat, but far from tetragonal.
4.1.5 | Catalytic effects
The Mizoroki–Heck reaction was chosen to investigate
the catalytic activity of 1. A model coupling reaction of
iodobenzene and methyl acrylate was implemented and
the reaction conditions in terms of temperature, solvent,
The peak positions of L are red-shifted in the Pt com-
plex: the peaks at 239 nm (ε = 50,290 L mol−1 cm−1),

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
11 of 18
FIGURE 9 The effect of bases on the Heck
reaction. Reaction conditions: 1.0 mmol
iodobenzene, 1.2 mmol methyl acrylate, 2 mmol
K3PO4, 0.5 mol% [PdII(qcq)(OAc)] (1), 130ꢀC,
4 hr, 3 ml solvent
FIGURE 10 The effect of solvent on the
Heck reaction. Reaction conditions: 1.0 mmol
iodobenzene, 1.2 mmol methyl acrylate, 2 mmol
K3PO4, 0.5 mol% [PdII(qcq)(OAc)] (1), 130ꢀC,
4 hr, 3 ml solvent, GC yield
TABLE 4 Optimization of reaction conditions for the Heck reaction of iodobenzene with methyl acrylate in the presence of catalyst (1)
Entry
Cat (mol %)
Base
Solvent
Temperature (ꢀC)
Time (h)
Yield (%)b
>99
1
2
3
4
5
6
7
1.5
1.25
0.5
0.5
0.5
0.5
0.5
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
H2O:PEG
H2O:PEG
H2O:PEG
H2O:PEG
H2O:PEG
H2O:PEG
H2O:PEG
130
130
130
130
130
130
130
24
24
24
12
6
>99
>99
>99
>99
2
80
4
>99
Abbreviation: PEG, polyethylene glycol.
aThe reaction was carried out with iodobenzene (1.0 mmol), methyl acrylate (1.2 mmol), base (2 mmol), and solvent (3.0 ml).
bGas chromatography yield.
bases, time and other critical parameters were optimized.
Initially, different bases, namely K2CO3, Tri-
ethanolamine, KOH, Na2CO3, NaOH, and K3PO4, were
tested in the model reaction and K3PO4 was found to be
the most effective (Figure 9). In the next step, different
solvents were used to find the optimal one, with H2O:
PEG showing superior results (Figure 10). In the final
step, temperature, time, and the amount of catalyst were

12 of 18
KIANI ET AL.
TABLE 5 Scope of the Mizoroki–Heck cross-coupling reaction
Entry
ArX
Olefin
Yield (%)
1
99
2
3
4
96
94
94
5
6
7
8
9
95
99
97
95
85
10
80
(Continues)

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
13 of 18
TABLE 5 (Continued)
Entry
ArX
Olefin
Yield (%)
11
12
81
79
13
14
15
16
17
18
19
88
65
60
48
43
35
39
(Continues)

14 of 18
KIANI ET AL.
TABLE 5 (Continued)
Entry
ArX
Olefin
Yield (%)
20
21
22
24
11
Trace
aThe reaction was carried out with aryl halide (1.0 mmol), olefin (1.2 mmol), and K3PO4 (2 mmol) in 3.0 ml H2O:PEG, catalyst (0.5 mol %) at 130ꢀC for 4 hr.
bIsolated yield.
investigated: using 0.5 mol % of catalyst at 130ꢀC and
4 hr reaction time was found to be optimal (Table 4).
Summarizing, the optimum reaction conditions involved
iodobenzene (1 mmol), methyl acrylate (1.2 mmol),
K3PO4 (2 mmol), and 1 (0.5 mol %) in H2O:PEG (3 ml) at
130ꢀC for 4 hr (Table 4, entry 7).
Encouraged by our initial studies, an investigation
into the generality and versatility of 1 in the Mizoroki–
Heck cross-coupling of aryl halides with olefins was
undertaken. As shown in Table 5 under the optimized
conditions, a diversity of aryl iodides, bromides, and
chloride containing electron-donating and electron-
TABLE 6 Comparison of catalytic activities of our catalyst with literature examples for the Heck reaction between iodobenzene and
methyl acrylate
Entry Catalyst
Condition
Yield Reference
1
2
3
Pd(OAc)2
Catalyst (0.5 mol %), H2O:DMSO, 80ꢀC, 2 hr
Catalyst (2.5 mol%), H2O:CH3CN, 80ꢀC, 5 hr
Catalyst (2.5 mol%), NMP:H2O, 160ꢀ C, 5 hr
97
84
97
[68]
[70]
[71]
Pd(OAc)2+ t-Bu-amphos
Di-2-pyridylmethylamine-based palladium
complexes
4
5
bis-(phenylsulfide)-Pd(II) complexes
Catalyst (0.1 mol%), NMP or DMF, 110ꢀC,
5–6 hr
Catalyst (0.5 mol %), H2O:PEG, 130ꢀC, 4 hr
92
[72]
[PdII (qcq)(OAc)] (1)
>99
Present
work
Abbreviations: t-Bu-amphos, t-buthyl-[4-(N,N-Dimethylamino)phenyl]di-tert-butylphosphine; DMF, Dimethylformamide ; DMSO, dimethyl sulfoxide; NMP,
N-Methyl-2-pyrrolidone ; PEG, polyethylene glycol.

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
15 of 18
withdrawing substituents reacted efficiently with methyl
acrylate and styrene under air at relatively mild
conditions of 130ꢀC to afford the desired cross-coupling
products in high yields.
The results show that the electronic properties of the
substituents on the aromatic rings of the starting mate-
rials had no significant effect on the reaction; aryl iodides
were, however, found to be more reactive than aryl bro-
mides.[66] Furthermore, the presence of electron-
withdrawing on aryl halides increased the yield of the
reaction.[67] Among aryl halides, aryl chlorides are ideal
substrates for coupling reactions owing to their availabil-
ity compared with their bromide or iodide counterparts.
The first step in the catalytic coupling reactions (oxida-
tive addition) disfavors aryl chlorides substrates because
of the high strength of the C–Cl bond. The most common
methods require high loadings of the palladium catalyst
and harsh conditions; they showed, however, only trace
or no activity with aryl chloride substrates. In order to
further investigate the efficiency and applicability of this
method, the cross-coupling reaction of aryl chlorides with
olefins was conducted under the same conditions. Aryl
chlorides proceeded smoothly in the presence of the same
amount of catalyst as used for aryl iodides and bromides.
It is important to note that the reported palladium cata-
lytic system in aqueous media, used in the Heck reaction,
was totally inactive for aryl chlorides.[10,68,69] Here we
report promising results for the Heck coupling reaction
of less reactive aryl chloride derivatives with olefins in
the presence of palladium catalyst for the first time. NMR
spectra showed that the trans product was obtained with
100% selectivity in all Heck olefination reactions. The
present catalytic method was compared with some proce-
dures published for the Mizoroki–Heck reaction of
iodobenzene and methyl acrylate in the literature, and
the results are shown in Table 6. Evidently, the reaction
conditions are mild, but the most important benefits of
this study are mild conditions, aqueous media, and a
green solvent.
FIGURE 12 Cyclic voltammogram of L in DMF at 298 K,
c ≈ 5 × 10–4, scan rate = 100 mV/s
FIGURE 13 Cyclic voltammogram of (1) in DMF at 298 K,
c ≈ 5 × 10–4, scan rate = 100 mV/s
FIGURE 11 Recyclability and reusability
study of complex 1 in the Mizoroki–Heck
coupling reaction

16 of 18
KIANI ET AL.
TABLE 7 MZI (mm) for the antimicrobial activity of L and 1, and 2
Compound
Hqcq
Salmonella
NIa
Klebsiella
NI
E. coli
10 0.6
22 0.24
21 0.34
NI
S. aureus
12 0.34
30 0.16
32 0.18
NI
B. cereus
11 0.72
25 0.38
26 0.32
NI
[Pd (qcq)(OAc)]
[Pt (qcq)(Cl)]
Pd (Oac)2
K2PtCl4
20 0.61
24 0.48
NI
15 0.54
17 0.64
NI
NI
NI
NI
NI
NI
Penicillin
DMSO
38 0.25
NI
16 0.35
NI
23 0.38
NI
44 0.33
NI
40 0.36
NI
Abbreviations: DMSO, dimethylsulfoxide; Hqcq, 8-(2-quinoline carboxamide)quinoline; NI, no inhibition.
Data are expressed as the mean standard deviation of samples analyzed individually in triplicate.
We also investigated the reusability of catalyst 1. For
this purpose, according to the insolubility of complex 1 in
water and PEG after each recycle, this complex was sepa-
rated from the reaction mixture by filtration and then
washed twice with distilled water and PEG, dried at 55ꢀC
for 2 hr, and reused for the Mizoroki–Heck cross-
coupling reaction of aryl halide, olefins, and K3PO4 at
130ꢀC for 4 hr. After four uses the reaction yield was
reduced to 82%, which indicates this catalyst has good
reusability. These results are presented in Figure 11.
Bacillus cereus and Staphylococcus aureus as Gram-
positive and Salmonella, Klebsiellap neumoniae and
Escherichia coli as Gram-negative species. The screening
results (MZI) are summarized in Table 7. While L does
not show significant activity, it is evident that complexes
1 and 2 exhibit antibacterial activity comparable to that
observed for standard antibiotic penicillin. The inertness
of the metal–ligand linkage presumably increases its
lipophilicity, cell permeability, and protection against
enzymatic degradation.[76] However, the exact mecha-
nism is unclear and further biological studies are neces-
sary to fully understand this behavior.[77]
4.1.6 | Electrochemical studies
The electrochemical behavior of L and 1 has been studied
by cyclic voltammetry in DMF solution at a scan rate of
100 mV/s, with 0.1 M TBAH as the supporting electrolyte
at a glassy carbon working electrode.
As expected and previously reported, carboxamide
ligands are electro-active in common organic solvents.[73]
As shown in the voltammogram of L (Figure 12), three
irreversible reduction waves of quinoline rings are
observed at −1.674, −2.192, and − 2.352 V, and are
shifted to more positive values for complex 1.[46] The
electrochemistry of 1 in DMF (Figure 13) shows an irre-
versible reduction process at −1.260 V which is attributed
to the reduction of the PdII/I center. This potential is in
5 | CONCLUSIONS
By using a benign procedure, the yield of the synthe-
sized ligand increased and the time of the reaction
decreased, and by employing the carboxamide ligand
PdII(qcq)(OAc) and PtII(qcq)Cl complexes were synthe-
sized, characterized, and assessed as catalysts in the
MizorokiHeck reaction for typical compounds. Hqcq
and the complexes were studied by X-ray diffraction
and their crystallization behavior and structures, espe-
cially a mixed crystal, are discussed. The electrochemi-
cal study of the Pd complex revealed a PdII/I reduction
process. The Pd complex catalyzed the Heck reaction
under mild conditions and with excellent yields in a
short reaction time under aerobic conditions in the
aqueous phase. The ligand and the Pd and Pt complexes
were also screened for their in vitro antibacterial activ-
ity: the complexes present strong biological activity
comparable to that of the antibiotic penicillin, while the
ligands are not active.
agreement
with
those
reported
in
related
Pd(II) complexes.[74,75] The last three irreversible reduc-
tion processes observed at −1.456, −2.029, and −2.218 V
are believed to be mainly ligand centered and due to the
reduction of quinoline rings, which are shifted to more
positive potentials in 1 relative to the free L.
4.1.7 | Antibacterial Properties
ACKNOWLEDGMENTS
L and the corresponding Pd(II) and Pt(II) complexes
1 and 2 were tested for antibacterial activity against
Support of this work by the Research Council of Sharif
University of Technology is gratefully acknowledged.

CATALYTIC AND ANTIBACTERIAL PROPERTIES OF CARBOXAMIDE PD/PT COMPLEXES
17 of 18
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CONFLICT OF INTEREST
There are no conflicts of interest.
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ORCID
Mojtaba Bagherzadeh https://orcid.org/0000-0003-
3009-3693
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How to cite this article: Kiani M,
Bagherzadeh M, Meghdadi S, Fadaei-Tirani F,
Schenk-Joß K, Rabiee N. Catalytic and
antibacterial properties of 3-dentate carboxamide
Pd/Pt complexes obtained via a benign route. Appl
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