Silver chloride supported on Vitamin B1 -Organometallic magnetic catalyst: synthesis, density functional theory study and application in A3-coupling reactions

Article abstract of DOI:10.1002/aoc.5725

A highly efficient Fe₃O₄@VitB₁–Ag(I) magnetic catalyst has been obtained using surface modification of Fe₃O₄. To this end, silver chloride was immobilized on Fe₃O₄ nanoparticles

Full text of DOI:10.1002/aoc.5725

Received: 18 January 2020
DOI: 10.1002/aoc.5725
Revised: 2 March 2020
Accepted: 16 March 2020
F U L L P A P E R
Silver chloride supported on Vitamin B -Organometallic
1
magnetic catalyst: synthesis, density functional theory
study and application in A3-coupling reactions
Naghmeh Esfandiary
| Farzane Pazoki
| Athar Nakisa | Kobra Azizi |
Iman Radfar
| Akbar Heydari
Tarbiat Modares University, PO Box
A highly efficient Fe O @VitB –Ag(I) magnetic catalyst has been obtained
14155-4838, Tehran, Iran
3
4
1
using surface modification of Fe O . To this end, silver chloride was
3
4
Correspondence
immobilized on Fe O4 nanoparticles via vitamin B1 biomolecules. The
3
Akbar Heydari, Department of Chemistry,
Faculty of Sciences, Tarbiat Modares
University, Tehran 14117-13116, Iran.
Email: heydar_a@modares.ac.ir
3
synthesized biocompatible magnetic catalyst was applied in an A -coupling
reaction in the presence of aldehyde, amine and phenyl acetylene under
solvent-free conditions and afforded the desired products in excellent yields.
Also, interactions between metal and ligand in the Fe O @VitB –Ag(I) were
3
4
1
studied using theoretical calculations.
K E Y W O R D S
3
A coupling, catalysis application, organometallic catalyst, Propargyl amines, silver-vitamin B
complex
1
1
| INTRODUCTION
Therefore, more studies are needed to establish the rel-
evance of these potential catalysts. Owing to the
importance of this issue, we have developed silver(I)–
NHC as main catalyst for the preparation of propa-
rgylic amines. Propargylic amines, products of one-pot
Since the first isolation of a crystalline stable carbine
by Arduengo in 1991, N-heterocyclic carbenes have
been widely employed as ligands, especially to
[1]
[
2]
prepare new metal-based catalysts.
One of the
multicomponent coupling reactions in the presence of
3
convenient synthetic methods to obtain NHC transition
metal complexes includes using its corresponding
Ag(I)–NHC complex as NHC transfer reagents, which
avoids the rigorous synthesis condition of free
carbenes. Lin and Wang, in 1998, reported the syn-
thesis of silver–NHCs by applying Ag O. Generally,
these silver complexes are readily synthesized by reac-
tion of their corresponding imidazolium salts with
silver(I) oxide, without working under an inert
aldehyde–alkyne–amine
coupling
(A -coupling),
are useful heterocyclic compounds and synthetically
[
8,9]
versatile key intermediates.
In recent years,
significant efforts have been made to develop one-
pot multicomponent reactions. Various catalytic
systems have been used to synthesize propargylic
[3]
[4]
2
[
10]
[11]
amines,
such
as
iron
silver(I)
and indium.
salts,
gold,
[
12]
[13]
[14]
Ag PW O
Moreover, there
3
12 40,
is still a need for the development of robust, widely
applicable methods that use inexpensive and eco-
friendly reagents for the synthesis of propargylic
amines.
[5]
atmosphere.
In addition to their transmetallation
ability, NHC–Ag(I) complexes are frequently used as
antimicrobial and anticancer agents. Silver(I)–NHCs
[
6]
are most prominent in the field of catalysis and there
are a few studies around their catalytic activity.
In this study, we used thiamine pyrophosphate,
having an imidazole agent as a carbene source.
[
7]
Appl Organomet Chem. 2020;e5725.
wileyonlinelibrary.com/journal/aoc
© 2020 John Wiley & Sons, Ltd.
1 of 12
https://doi.org/10.1002/aoc.5725

2
of 12
ESFANDIARY ET AL.
Thiamine diphosphate is an active form of vitamin B1
which is an essential organic cofactor in all living sys-
tems and vital for general metabolism amongst all
2 | EXPERIMENTAL
2.1 | Chemicals, instrumentation and
analysis
[15]
organisms.
Thiamine diphosphate contains three
versatile functional groups: a diphosphate-terminated
side-chain, a five-membered thiazolium ring and a six-
All purchased chemicals were of analytical grade and
used without further purification. FT-IR spectra were
obtained in the region 400–4000 cm− using a Nicolet
IR100 instrument with spectroscopic-grade KBr. the mor-
phology of the powder catalysts was determined by SEM
image on Philips XL 30 and S-4160. The magnetic proper-
[16]
membered aminopyrimidine ring.
Thus, it is chal-
1
lenging to investigate its potential activity in various
organic reactions. Thiamine has gained paramount
importance owing to its potential catalytic activity in
[17]
organic transformation.
Additionally, the immobilization of active biomole-
cules on the surface of nanoparticles with covalent
interaction is a remarkable synthetic approach. We
tried to overcome this challenge by stabilizing phos-
phate agents on the magnetic surface. Magnetic
materials have attracted great attention owing to their
diverse applications in various reactions. Moreover, the
magnetic nanoparticles have numerous benefits
such as good accessibility, low cost, simple preparation,
low toxicity, high efficiency and recoverable
ties
were
measured
with
a
vibrating
magnetometer/alternating gradient force magnetometer
(MDCo., Iran; www.mdk-magnetic.com). TGA was per-
formed using a thermal analyzer with a heating rate of
ꢀ
−1
ꢀ
20 C min over the temperature range 25–1100 C under
flowing compressed nitrogen.
2.2 | Preparation of catalyst
[18]
properties.
Superparamagnetic Fe O nanoparticles were prepared
3
4
Herein, we report a renewable and environmentally
safe metal complex (Scheme 1) as a robust, efficient
and environmentally friendly catalyst to perform A -
according to a conventional co-precipitation method.
FeCl ·6H O (10 mmol) and FeCl ·4H O (5 mmol) salts
3
2
2
2
3
were dissolved in 40 ml of deionized water and were
stirred vigorously (800 rpm) for 2 min at room tempera-
ture. Then ammonia solution (25% w/w) was added
dropwise to produce an alkaline medium (pH about 11).
The obtained black suspension was stirred vigorously for
1 h at room temperature and then was refluxed for 6 h.
The synthesized magnetic Fe O nanoparticles were sepa-
coupling reaction under mild conditions with high
yields. The structure of the magnetic catalyst was
characterized by scanning electron microscopy (SEM),
X-ray Powder Diffraction (XRD), Fourier transform
infrared (FT-IR), thermogravimetric analysis (TGA),
Vibrating sample magnetometry (VSM) and energy-
dispersiveX-ray spectroscopy (EDX). This catalyst can
be reused and recovered five times without any
significant loss of catalytic activity Also, the density
functional theory (DFT) model was used to show all of
the intramolecular interactions of metallic present in
the Fe O @VitB –Ag(I) complex.
3
4
rated from the medium by applying an external magnet
and washed several times with water and ethanol.
Prepared nanoparticles were poured into the flask,
then 2.1 mmol of phosphorus vitamin B (thiamine pyro-
1
phosphate chloride) was dissolved in methanol and
added to the flask. After that, the mixture was placed in
3
4
1
SCHEME 1 Catalyst synthetic procedure

ESFANDIARY ET AL.
3 of 12
SCHEME 2 Synthesis of propargyl amine in the presence of
Ag (I)–VitB @Fe O
1 3 4
an ultrasonic bath for 1 h at room temperature. Finally,
Fe O @VitB particles were decanted and dried in an
3
4
1
oven overnight.
3 4
FIGURE 2 VSM curve of Fe O (orange curve) and
To achieve the correct amount of vitamin B loaded
3 4 1
Fe O @VitB –Ag(I) (blue curve)
1
onto Fe O nanoparticles, determination of the acidity of
3
4
vitamin B with back-titration was used. Thus, 100 mg
(equal to 0.4 mmol supported vit B ) in dry CH Cl . The
1 2 2
1
sample was added to 5 ml (excess) 0.1 M NaOH solution.
After 10 min of sonication two drops of phenolphthalein
pH-indicator were added to the vessel. Back-titration was
accomplished by first changing the color of solution with
the addition of standardized 0.1 M HCl solutions. To find
mixture was continuously stirred at room temperature
for 24 h. After that, the resulting superparamagnetic par-
ticles [Fe O @VitB –Ag(I)] were first separated from the
3
4
1
medium, then washed with tetrahydrofuran several times
ꢀ
and dried at 60 C overnight. The synthesis procedure is
the amount of base that reacted with the vitamin B , the
shown in Scheme 2.
1
unreacted base (or consumed HCl: 0.06 mmol) was sub-
tracted from the primary amount of base (0.1 mmol). The
−1
3
acidity value was obtained as 0.4 mmol g by adding
.6 ml HCl, which is equal to the quantity of supported
2.3 | The typical procedure for the A -
0
coupling reaction using Fe O @VitB1–Ag
3
4
vitamin B . In order to the number of moles of excess
(I)
1
NaOH left after the reaction was determined, the follow-
ing equation was used:
A catalytic amount of Fe O @VitB –Ag(I) (40 mg) was
3
4
1
added to a mixture of aryl aldehyde (1 mmol), amine
ꢀ0
ꢁ
(
1.1 mmol) and phenyl acetylene (1.2 mmol). The mix-
:04 mmol 0:1 g
x = 0:4mmolg−
1
ꢀ
ture was stirred under solvent-free conditions at 100 C.
After completion of the reaction (~14 h), Thinlayer
chromatography (TLC) test was done to monitor and
determine the end-point of the reaction. The resulting
product was purified by column chromatography on
X
1 g
In the final stage, the metalation reaction was carried
out by adding Ag O (0.4 mmol) to 1 g Fe O @VitB
2
3
4
1
FIGURE 1 FT-IR spectra of Fe
3
O
4
(dark blue curve), Fe
3
O
4
1 3 4 1
@VitB (purple curve) and Fe O @VitB –Ag(I) (light blue curve)

4
of 12
ESFANDIARY ET AL.
3 4
FIGURE 4 TGA of Fe O @VitB1−Ag(I)
curve), Fe O @VitB (purple curve) and Fe O @VitB –
3
4
1
3
4
1
Ag(I) (light blue curve) are depicted in Figure 1. The
−
1
spectrum of Fe O (a), shows a band around 560 cm
3
4
which can be attributed to the stretching vibrations of
the Fe–O bond. The broad peak at 3400 cm− is related to
1
–
OH. In the spectrum for thiamine pyrophosphate
−
1
FIGURE 3 SEM image of Fe
3
O
4
@VitB
1
–Ag(I)
functionalized Fe O (b), the peak at 1053 cm can be
3 4
associated with vibrations of the symmetric stretching of
P–O bond. Bands around 1435 and 1655 cm− can be
related to O=P–OH in phosphate groups. The peak at
1539 cm− can be ascribed to the C=N band stretching
1
silica gel (eluant: n-hexane–ethyl acetate) to give the
corresponding A -coupling product. The FT-IR and
HNMR of products are given in supporting information.
3
1
frequency. Also, small bands that are depicted around
900 cm− are related to asymmetric and symmetric C–H
1
2
3
3
| RESULTS AND DISCUSSION
.1 | Characterization of the catalyst
stretching, and bands in the range of 1100–1500 are
related to stretching vibrations of thiazolium ring in thia-
mine pyrophosphate molecules. In the Fe O @VitB –Ag
3
4
1
(
I) spectrum (c), a shift in thiazolium ring signal is
To confirm the synthesis of the catalyst, the structure was
characterized using some spectroscopic and microscopic
techniques, namely FT-IR spectroscopy, VSM, SEM, EDX
and TGA. FT-IR spectroscopy is used to investigate the
structure catalysts by monitoring each change in the pro-
observed, which is proof of Ag immobilization.
To investigate the magnetic properties of the
Fe O @VitB –Ag(I), VSM analysis was used. A graph of
3
4
1
−1
magnetization (emu g ) as a function of applied field
(Oe) was drawn (Figure 2) with confined field (−10,000
to +10,000 Oe) at room temperature. The magnetization
of bare Fe O nanocrystals (orange curve) was 56 emu
cess of synthesis. FT-IR spectra of Fe O4 (dark blue
3
3
4
−
1
TABLE 1
surface of Fe
spectroscopy
Weight percentage of various elements on the
3 4
O @VitB1–Ag(I)from energy-dispersiveX-ray
g
at room temperature. Nonetheless, the magnetization
of Fe O @VitB –Ag(I) (blue curve) decreased to
3
4
1
−1
4
1.87 emu g owing to vitamin coating on the surface of
the magnetic Fe O nanoparticles.
Element
Wt%
42.65
3.91
Atom%
3 4
VSM shows the hysteresis loops of the Fe O @VitB –
3
4
1
C
64.39
2.22
Ag(I) at room temperature. Zero remanence and coerciv-
ity of the magnetization curve demonstrate the super-
paramagnetic properties. With the Fe O @VitB –Ag
N
O
S
17.31
1.64
19.71
2.78
3
4
1
(
I) dispersed in CH Cl , an external magnetic field can
2 2
Cl
P
2.56
1.32
immediately gather the particles, then with slight shak-
ing, they can be promptly re-dispersed. The results show
that the particles display good magnetic characteristics
and can be applied as a magnetic catalyst.
To investigate surface morphology and size of the par-
ticles, SEM analysis was used. The SEM image of the
3.43
2.01
Fe
Ag
17.56
10.93
5.73
1.85
1
00.00
100.00

ESFANDIARY ET AL.
5 of 12
3 4 1
FIGURE 5 The XRD pattern of Fe O @VitB -Ag(I)
modified catalyst revealed that the samples possess spher-
ical morphology and uniform particles. The approximate
size of the particles is 120–140 nm (Figure 3).
To deduce the composition of the synthesized cata-
lyst, EDX was carried out (Table 1). The EDX analysis
shows no other peaks except for Fe O @VitB –Ag
SCHEME 3 Design of reaction for optimizing conditions
3
4
1
(
I) nanoparticles (Fe, Ag, S, C, P, O and Cl), which dem-
TABLE 3
Screening of the catalysts
onstrates the high purity of the composites. This implies
Entry
Catalyst
Time (h)
Yield (%)
—
that the silver–carbene complex is supported on the sur-
face of Fe O nanoparticles.
1
2
3
4
—
14
14
14
14
3 4
The TGA technique is valuable to find out the mois-
ture content and percentage of inorganic and organic
components in materials depending on temperature
Fe
3
Fe
3
Fe
3
O
4
O
4
O
4
Trace
Trace
89
@ VitB1
@VitB1–Ag(I)
increase. Figure
4
shows the TGA spectra of
TABLE 2
Optimization of reaction conditions for propargyl amine synthesis
ꢀ
Entry
Catalyst
Solvent
Amount of catalyst
Temperature ( C)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
—
—
—
20
20
20
20
20
20
20
30
40
40
40
50
100
80
24
14
14
14
14
14
14
14
14
14
14
14
14
—
73
70
73
62
65
69
75
79
84
89
88
88
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
3
3
3
3
3
3
3
3
3
O
O
O
O
O
O
O
O
O
4
4
4
4
4
4
4
4
4
@VitB
@VitB
@VitB
@VitB
@VitB
@VitB
@VitB
@VitB
@VitB
1
1
1
1
1
1
1
1
1
–Ag
–Ag
–Ag
–Ag
–Ag
–Ag
–Ag
–Ag
–Ag
3
CH CN
H
2
O
80
CH
2
Cl
2
80
DMSO
80
Tetrahydrofuran
80
Methanol
80
—
—
—
—
—
—
80
80
10
11
12
13
80
Fe
3
O
4
@VitB
1
–Ag
100
120
100
Fe
3
3
O
4
@VitB
@VitB
1
1
–Ag
–Ag
Fe
O
4

6
of 12
ESFANDIARY ET AL.
TABLE 4
Synthesis of various propargyl amine derivatives
Entry
Substrate
Product
Yield (%)
1
83
2
78
3
88
4
95
5
80
6
89

ESFANDIARY ET AL.
7 of 12
TABLE 4 (Continued)
Entry
Substrate
Product
Yield (%)
7
83
72
74
8
9
Fe O @VitB –Ag(I). the first step by ~12% weight loss
only achieve high efficiency but also recover the catalyst
(Scheme 3).
3
4
1
ꢀ
under 200 C is related to the loss of water and humidity.
The second phase involves degradation of the organic
portion, around 17%, which is disintegrated starting at
To determine the optimized conditions, we investi-
gated various solvent effects, even solvent-free conditions.
Slightly lower yields were obtained using tetrahydrofuran
and Dimethyl sulfoxide (DMSO) (Table 1, entries 5 and
6). The corresponding products were moderately
obtained in dichloromethane, water and methanol
(Table 1, entries 4, 3 and 7). The reaction being carried
out in acetonitrile achieved acceptable yield but solvent
free conditions was determined as optimum. By optimiz-
ing temperature, we determined that the best tempera-
ꢀ ꢀ
<
200 C and finishing >356 C. During the step, the struc-
ture of the catalyst shrinks because the molecules are
broken down by increasing temperature. Furthermore,
according to thermal analysis, the catalyst was stable up
ꢀ
to 200 C.
XRD pattern was investigated to determine the crys-
talline structure of the Fe O @VitB -Ag(I), (Figure 5),
3
4
1
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
diffraction peaks at around 35 , 42 , 51 , 63 , 67.8 and
7
ꢀ
ꢀ
4.7 corresponding to (220), (311), (400), (422), (511),
ture was 100 C.
and (440) are quite identical to characteristic peaks of the
cubic phase of Fe3O4 (JCPDS19–629).
For the last step, the amount of catalyst was opti-
mized, the reaction was carried out in the presence of
40 mg of catalyst under the same conditions (Table 2,
entry 11) and a further increase did not affect the pro-
gress of the reaction or time. The model reaction was car-
ried out with Fe O , Fe O @VitB , Fe O @VitB –Ag
3
.2 | Catalyst activity
3
4
3
4
1
3
4
1
3
The A -coupling reaction was optimized, using benzalde-
hyde, amine and phenylacetylene (Scheme 2) and all
results are summarized in Table 1. The reaction was car-
ried out in the presence of catalyst, but the result was not
satisfactory. For the next step, we tested Fe O @VitB –
Ag(I) as a heterogeneous catalyst and obtained excellent
results. With immobilizing silver–carbene complex on
the surface of magnetic Fe O nanoparticles we could not
(I) and in the absence of the catalyst. This reaction had
low yield in the presence of Fe O and Fe O @VitB
1
3
4
3
4
(Table 3, entries 2 and 3). Also, there was no product in
the absence of the catalyst (Table 3, entry 1).
Using this procedure, we tried to synthesize various
derivatives of propargyl amine using different aldehydes
with secondary amines and phenylacetylene as model
substrates. The achieved products are listed in Table 4.
3
4
1
3
4

8
of 12
ESFANDIARY ET AL.
SCHEME 4 Proposed mechanism of propargyl amine synthesis
3
.3 | Proposed mechanism
as the formation of iminium ion in situ from aldehydes and
secondary amines. Then the silver(I)–acetylide intermediate
was added to the iminium ion to give the corresponding
propargyl amine and regenerate the Fe O @VitB –Ag
A tentative mechanism is proposed as shown in Scheme 4.
An intermediate π-silver–alkyne was formed first, making
the alkyne proton more acidic for further abstraction as well
3
4
1
(I) catalyst for a further sequence of reactions.
FIGURE 6 Recyclability of catalyst

ESFANDIARY ET AL.
9 of 12
3
.4 | Reusability of catalyst
reported catalysts in the literature. It can be seen in
Table 5 that the present catalyst showed good catalytic
activity. Noticeably, this new catalyst is comparable in
terms of price, eco-friendliness, reusability, commercially
available materials, easy preparation and facile
separation.
Also, the reusability of the Fe O @VitB –Ag(I) catalyst
was evaluated using pyrrolidine, benzaldehyde and
phenylacetylene as model reaction. After
accomplishing the reaction, the superparamagnetic cat-
alyst was separated from the medium, as usual, by an
external magnet, then washed and dried and used for
another reaction run. The catalyst was reused until the
results were not satisfactory. In this way, the recycla-
bility of our synthesized catalyst was examined
3
4
1
a
4 | COMPUTATIONAL
4.1 | Computational details
(Figure 6). The catalyst showed excellent results for
five repeat cycles, after which there was a deterioration
in its catalytic activity.
We have reported a quantitative description for metal–
ligand interactions in the Fe O @VitB –Ag(I) by
3
4
1
The results obtained for the click reaction under the
optimized conditions were compared with previously
employing DFT and the quantum theory of atoms in mol-
ecules (QTAIM) was performed to describe the covalent
3
TABLE 5
Comparison of the catalytic efficiency of Fe
3
O
4
@VitB1–Ag(I) with the previously reported catalytic systems in A -coupling
reactions
Entry
Catalyst
Reaction conditions
Yield (%)
[
20]
1
AgI
Benzaldehyde (1.0 mmol), piperidine (1.2 mmol)
70
and phenylacetylene (1.5 mmol) 1.5 mol % AgI,
ꢀ
1
00 C, water (1 ml)
[
21]
2
{CuCl[2,5-bis(2-thienyl)-1-phenylphosphole]2}
3 mmol of benzaldehyde; 3.3 mmol of amine;
.5 mmol of alkyne and 0.1 mol% of catalyst
92
4
{
1
CuCl[2,5-bis(2-thienyl)-1-phenylphosphole]2},
00 C, 5 h
ꢀ
[
[
22]
23]
3
4
5
Cu
pip = (2-picolyliminomethyl)pyrrole anion]
2
(pip)
2
Benzaldehyde (1.0 mmol), piperidine (1.0 mmol)
99
93
[
and phenylacetylene (1.2 mmol) in toluene
ꢀ
(
3 ml), 100 C
Fe
3
3
O
4
4
@PT@Au
Benzaldehyde (1 mmol), amine (1.5 mmol),
alkyne (1.5 mmol), H O (2 ml), catalyst (10 mg,
.01 mol%), 1 day
2
0
Fe
O
@VitB1–Ag(I)
Benzaldehyde (1 mmol), piperidine (1.1 mmol)
95
ꢀ
and phenyl acetylene (1.2 mmol), 50 C, 14 h
FIGURE 7 Complete molecular graphs of compounds 1 and 2 obtained with b3lyp/6-21 g electron density functions

10 of 12
ESFANDIARY ET AL.
TABLE 6
Some typical values of bond orders and distances in
4.2 | Computational assessment
.2.1 | QTAIM
compounds 1 and 2 calculated at B3LYP/6-21G level of theory
4
Bonded or
interacting atoms
Bond
order
Bond length or
distance (Å)
QTAIM computations were employed for the quantitative
description of metal–ligand interactions of the silver (I)
Compound 1
O3–P1
0.34
0.25
0.15
1.06
1.06
1.55
1.60
1.71
1.42
1.85
supported on vitamin B -functionalized magnetic organo-
1
O2–P1
metallic catalyst [Fe O @VitB –Ag(I) compound 2].
3
4
1
O5–P1
The optimized geometries of compounds 1 and 2 with
the assigned labels of the desired atoms are represented
in Figure 7. We also list in Table 6 Ag53–C27, Ag53–Cl54,
Fe12–O3, O5–P1, O3–P1, O2–P1, C27–S29 and N28–C27
bond lengths and bond order for compounds 1 and 2.
The data in Table 5 show that the bond order of O2–
P1, O5–P1, N28–C27 and C27–S29 increased and bond
length decreased in compound 1 compared with com-
pound 2. It seems that these bonding interactions were
strengthened after compound formation.
N28–C27
C27–S29
Compound 2
O3–P1
0.89
1.25
0.82
1.36
1.32
0.46
0.43
0.58
1.55
1.49
1.58
1.35
1.72
2.20
2.48
1.82
O2–P1
O5–P1
N28–C27
C27–S29
Ag53–C27
Ag53–Cl54
Fe12–O3
In the next step, investigation of the nature of metal–
ligand interactions was carried out using the QTAIM
method. Figure 8 shows QTAIM molecular graphs of
compounds 1 and 2 with critical points. Calculated
parameters such as, electron density ρ , Laplacian r2ρ ,
C
C
total electronic energy density G , total electronic energy
C
density V , and total electronic energy density H are
C
C
and electrostatic character of bonds in Fe O @VitB –Ag
listed in Table 7. Calculated values of ρb at O2–P1, O5–
P1, N28–C27 and C27–S29 were increased.
3
4
1
(
I) and Fe O @VitB . In this regard, the simplified struc-
3 4 1
tures of ligand (VitB ) and compound [Fe O @VitB –Ag
The value of ρ > 0.1 au and negative r2ρ value at
1
3
4
1
C
C
(I)] were considered as compounds 1 and 2. Geometries
N28–C27 and C27–S29 indicate the covalent character of
these chemical bonds in compounds 1 and 2. Values of
ρC < 0.1 au and the relatively small and positive value of
of all structures were optimized using B3LYP model
chemistry with the 6-21G basis sets. All DFT computa-
[19]
tions
software.
were carried out employing the GAMESS
r2ρ at Ag53-I54 indicate the electrostatic interaction.
C
[16]
r2ρ > 0 and H < 0 at O3–P1 and O2–P1 in compound
C
C
FIGURE 8 Complete molecular graphs of compounds 1 and 2 obtained with QTAIM analysis of b3lyp/6-21 g electron density
functions. Red, oxygen; yellow, sulfur; blue, nitrogen; brown, iron; green, chlorine; white, silver; and gray, hydrogen

ESFANDIARY ET AL.
11 of 12
TABLE 7
The calculated mathematical properties of compounds 1 and 2
2
Compound
Site
ρ
c
= ρ
c
G
C
V
C
H
C
1
O3–P1
0.18
0.16
0.13
0.27
0.14
0.19
0.21
0.18
0.28
0.21
0.08
0.05
0.12
0.92
0.36
−0.10
−0.09
−0.08
−0.31
−0.07
−0.11
−0.12
−0.11
−0.32
−0.17
−0.01
−0.006
−0.05
−0.05
0
−0.15
−0.09
0.16
O2–P1
O5–P1
0.32
0.24
N28–C27
C27–S29
O3–P1
−0.48
−0.08
1.11
0.73
0.42
0.16
0.09
0.16
0.06
O2–P1
1.48
−0.11
−0.02
0.76
−0.23
−0.13
0.44
O5–P1
0.96
N28–C27
C27–S29
Ag53–C27
Ag53–Cl54
Fe12–O3
−0.47
−0.40
0.28
2
0.45
0.27
−0.06
−0.038
0.94
−0.07
−0.032
0.88
0.20
0.59
1
and O2–P1, O5–P1 and Ag53–C27 indicate partial cova-
ORCID
lence. r2ρ > 0 and H > 0 at Fe12–O3 indicate van der
Naghmeh Esfandiary https://orcid.org/0000-0002-8413-
9952
C
C
Waal's interactions.
Farzane Pazoki https://orcid.org/0000-0001-8616-5591
Iman Radfar https://orcid.org/0000-0003-4965-1982
5
| CONCLUSION
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