Pd/Cu-Free Cobalt-Catalyzed Suzuki and Heck Using Green Bio-Magnetic Hybrid and DFT-Based Theoretical Study

Article abstract of DOI:10.1007/s10562-020-03487-3

Abstract: Several highly efficient and magnetically recyclable cobalt catalytic systems were prepared using magnetic chitosan and some safe and available organic compounds (Co-ligand@MNPs/Ch). The structure of these nanocomposites was confirmed by various physicochemical techniques such as FT-IR, XRD, TGA, VSM, TEM, SEM, CHNS and ICP-OES. These nano composites exhibit remarkable catalytic efficiency for Suzuki and Heck cross-coupling reactions in mild and green reaction conditions. The facile accessibility of starting materials, possible performance in air and eco-friendly conditions are merits of our catalysts. In addition, to describe and go insight to role and effect of ligands present in these catalysts, electrostatic interactions, density functional theory (DFT) model in molecular method were employed. Graphic Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-020-03487-3

Catalysis Letters
https://doi.org/10.1007/s10562-020-03487-3
Pd/Cu‑Free Cobalt‑Catalyzed Suzuki and Heck Using Green
Bio‑Magnetic Hybrid and DFT‑Based Theoretical Study
Abdol R. Hajipour1,2 · Zahra Khorsandi1 · Mehnoosh Ahmadi3 · Hamidreza Jouypazadeh1 · Bahareh Mohammadi1 ·
Hossein Farrokhpour1
Received: 17 September 2020 / Accepted: 1 December 2020
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature 2021
Abstract
Several highly efcient and magnetically recyclable cobalt catalytic systems were prepared using magnetic chitosan and
some safe and available organic compounds (Co-ligand@MNPs/Ch). The structure of these nanocomposites was confrmed
by various physicochemical techniques such as FT-IR, XRD, TGA, VSM, TEM, SEM, CHNS and ICP-OES. These nano
composites exhibit remarkable catalytic efciency for Suzuki and Heck cross-coupling reactions in mild and green reaction
conditions. The facile accessibility of starting materials, possible performance in air and eco-friendly conditions are merits
of our catalysts. In addition, to describe and go insight to role and efect of ligands present in these catalysts, electrostatic
interactions, density functional theory (DFT) model in molecular method were employed.
Supplementary Information The online version of this article
(https://doi.org/10.1007/s10562-020-03487-3) contains
supplementary material, which is available to authorized users.
* Abdol R. Hajipour
haji@cc.iut.ac.ir
* Zahra Khorsandi
khorsandiz_91@yahoo.com
* Hossein Farrokhpour
farrokhphossein@gmail.com
1
Department of Chemistry, Isfahan University of Technology,
8415683111 Isfahan, Iran
2
Department of Neuroscience, Medical School, University
of Wisconsin, 1300 University Avenue, Madison,
WI 53706-1532, USA
3
Department of Chemical Engineering, Shahreza Branch,
Islamic Azad University, Shahreza, Iran
Vol.:(0123456789)
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A. R. Hajipour et al.
Graphic Abstract
Keywords Suzuki reaction · Heck reaction · Cobalt · Theoretical study · Nanoparticles
catalysts in Suzuki coupling reaction was also described by
Bhat et al. [16]. In addition, Duong et al. studied cobalt-
catalyzed cross-coupling reactions of arylboronic esters and
aryl halides [17, 18]. In other report, Suzuki cross-coupling
of aryl halides with alkyllithium-activated arylboronic pina-
colate esters in the present of cobalt catalyst were investi-
gated [19].
1 Introduction
One of the most frequently employed methods for car-
bon–carbon bond formation in organic synthesis is the
Suzuki cross-coupling reaction [1]. This reaction are applied
commercially for the production of a range of materials
including the active pharmaceutical ingredients [2–4]. The
use of palladium metal in Suzuki cross-coupling reactions,
even though its good catalytic activity, is an undesirable
afair due to its rarity, expensively and toxicity. Standard
limits of palladium traces in pharmaceuticals have been set
usually as ppm level.
Despite the high advantages of these catalytic systems
such as low-cost, availability and efciency, they sufer
from some drawbacks like un-reusability. Therefore, using
a novel catalytic system that can overcome this limitation is
required. Herein, applying heterogeneous cobalt catalysts
prepared from eco-friendly and nontoxic commercially
available precursors in cross-coupling reaction of aryl hal-
ides and phenylboronic acid have been reported. To the best
of our knowledge, Suzuki reactions employing heterogonous
cobalt catalyst have not been reported previously.
Therefore, there is a growing incentive to replace it with
more suitable options based on the earth’s abundant metals
[5]. In this regard, frst-row transition metals are particularly
attractive, including Suzuki cross-coupling reactions in the
presence of nickel and iron catalysts [6–14]. Very recently,
a few studies on the use of cobalt catalysts in this coupling
reaction have been reported such as coupling of aryl trifates
with aryl boron pinacol esters using a cobalt PNP-pincer-
based catalyst [15]. Application of cobalt pincer-based
One of the other most important reaction in organic
synthesis is the Heck cross-coupling reaction which have
used in the pharmaceutical, agrochemical and fne chemical
industries [20]. The traditional catalytic system for Heck
1 3

Pd/Cu-Free Cobalt-Catalyzed Suzuki and Heck Using Green Bio-Magnetic Hybrid and DFT-Based…
couplings include the use of palladium. However, due to
its high cost and toxicity, usage of palladium-free catalytic
systems is more interesting in view of modern organic syn-
thesis. Nevertheless, many diferent synthetic methods based
on palladium-free catalysts applying nickel [21, 22]. Copper
[23–25], iron [26–28] and cobalt [29, 30] have been reported
for the Heck reaction. Among these, cobalt is readily avail-
able, non-toxic, low-cost and stable with powerful catalytic
activities. A few reports about cobalt catalysts applications
in the Heck coupling reaction are available. For example,
in 2009, Qi et al. reported cobalt nanoparticles as catalyst
for the Heck cross-coupling reaction. Notably, in spite of
harsh reaction conditions, the scope of aryl halides was not
described [31]. Recently, Zhu et al. have applied uniform
Co–B amorphous alloy nanoparticles catalyst in the Heck
reaction [32].
Encouraged by our previous studies on cross-coupling
reactions with successful experiences in using cobalt-cata-
lysts [33–35], a series of heterogeneous cobalt catalysts was
introduced and their applications in Suzuki and Heck cross-
coupling reaction was studied and compared.
Generally, the nanoparticle-based catalytic systems
exhibit higher activity than their corresponding bulk mate-
rials because of their large surface-to volume ratio [36].
Scheme 1 Magnetic chitosan supported ligands used for synthesis of
However, aggregation of the nanoparticles form larger, bulk
particles and, so, their catalytic activities are reduced. It can
be avoided by using suitable stabilizers or protecting agents
[37–39].
catalysts
their efciency in Heck and Suzuki reactions was studied
and compared together.
For preparation of heterogonous catalysts, various organic
and inorganic supports, containing charcoal, inorganic silica,
alumina and synthetic polystyrene, has already been used.
In this regard, applying an environmentally friendly poly-
mer support is very promising. Chitosan, the N-deacetylated
derivative of chitin, is a polysaccharide with surface-rich
hydroxylic groups that make macro chelating ligand [40, 41].
In order to improve pore size, mechanical strength, chemical
stability, hydrophilicity and bio-compatibility, modifcations
by cross-linking agents have been applied, using with vari-
ous organic ligands. The combination of magnetic and bio-
logically properties provide a novel hybrid nanomagnetic-
biomaterial for varied catalytic applications [42–44].
Considering to our fndings, efectiveness of used organic
ligands promoted us to more studies of their nature. Several
fundamental questions exist, such as: (i) What is the nature
of the interface between the cobalt and the surface ligands?
(ii) Which ligands bind most strongly to cobalt? Answering
such questions and improving our understanding about efect
of various ligands is valuable for designing nanostructures;
so, these were probed by Ab initio calculations.
Initially, the bio-magnetic cobalt catalyst was prepared.
At frst, NH2 functional group of chitosan was reacted with
selected ligands via an amide, imine and C–N bond forma-
tion. Then, the resulting functionalized chitosan was treated
with a cobalt salt to form the complex, the synthesis process
for one of them (methyl histinate) was illustrated in Scheme
S1 as example. The FT-IR (Figures S1-S6), thermo gravi-
metric analysis (TGA), and elemental analysis was used to
monitor these processes in several synthesized catalysts.
The FT-IR spectrum of MNPs/Ch was given in supple-
mental data (Figure S1). Chitosan exhibited characteristic
absorption bands at 3589 cm−1 due to –NH and/or –OH
stretching vibrations and at 2933 and 2852 cm−1 corre-
sponded to C–H stretching vibration of copolymer of chi-
tosan (Figure S1, a). The band assigned to CH2OH of chi-
tosan appeared at 1383 cm−1, while the band at 1092 cm−1
2 Results and Discussion
Herein, a series of functionalized magnetic chitosan was
prepared using various green and available ligands includ-
ing methyl histidinate (His), methyl phenylalaninate (Phe),
cyanuric chloride (Cy) and salicylaldehyde (Sa) (Scheme 1).
The cobalt was tagged to these bio nanomagnetic mate-
rials and denoted as Co-ligand@MNPs/Ch. To investigate
the electronic and steric efect of various organic ligands in
catalytic activity and their ability to hosting cobalt species,
1 3

A. R. Hajipour et al.
accounted to O–H bending [45, 46]. The band at 1151 and
803 cm−1 corresponded to C–O–C antisymmetric stretch-
ing and glycoside linkage of saccharide structure, respec-
tively [47, 48]. Similarly, the FT-IR spectrum of magnetic
nanoparticles (Fe3O4) demonstrated bands respectively
at 3434, 1631, 1390 and 570 cm−1 (Figure S1, b). The IR
spectrum of MNPs/Ch in comparison to pure chitosan and
magnetite clear shifting of the absorption spectra were
recorded in MNPs/Ch. The -NH, -OH and -CH stretching
vibrations of chitosan molecule were shifted to 3431, 2927
and 2860 cm−1, respectively due to the binding of Fe3O4
nanoparticles with chitosan (Figure S1, c). In the fnal cata-
lyst (Figure S1, d), no signifcant diference with magnetic
chitosan was observed. The MNPs/Ch can be introduced
as good host for metal species, in MNPs/Ch, the chitosan
prevents magnetic nanoparticles from aggregation.
Cs) was studied by feld emission scanning (FE-SEM) (Fig-
ures S14-S16). The energy dispersive X-ray (EDX) and anal-
ysis mapping results, obtained from SEM analysis for Co-
His@MNPs/Ch (Figure S14) clearly confrmed the surface
morphology of catalyst. Further characterization of catalysts
was performed by transmission electron microscopy (TEM)
(Figures S17-S21) (Fig. 1) with size distribution of nanopar-
ticles for each catalyst.
Further characterization of the catalyst was performed via
the magnetization properties of catalysts which their cure
is shown in Figures S22–S26. The magnetization value for
Fe3O4 is 69.4 emu g−1 and for each catalyst was obtain. The
investigation proved the paramagnetic behavior of our mag-
netic catalysts was meaningfully lower than that of the bulk
magnetite due to the coating of magnetic nanoparticles with
chitosan and ligands.
The FT-IR spectrum of His@MNPs/Ch shows signifcant
bonds that confrmed their structures (Figure S3), such as
bonds of 1676 cm−1 (C=O amide), 1725 cm−1 (C=O ester),
2933 (C–H) and 3436 cm−1 (N–H stretching vibration).
The amount of organic moieties in catalysts was deter-
mined by TGA and elemental analysis. The weight loss of
MNPs/Ch, MS@MNPs/Ch and His@MNPs/Ch between 30
and 800 °C was determined using TGA, which is an irre-
versible process because of thermal de-composition. The
TGA plots of synthesized catalysts depict a two main step
thermal decomposition. The frst step of weight loss related
to the removal of physically adsorbed water, whereas the
main weight loss in the second step was corresponded to
the removal of organic moieties on the surface (Figures S7,
S8). The TGA and elemental analysis outcomes of samples
are summarized in Table S1. The total amount of the organic
moieties on His@MNPs/Ch was about 0.36 mmol g−1 which
show good agreement with elemental analysis. The amount
of the organic moieties of Ph@MNPs/Ch, Cy@MNPs/Ch
and Sa@MNPs/Ch which probed by elemental analysis was
also given in Table S1.
The nitrogen adsorption method (BET analysis) used for
characterization of the porous materials and pore structure
(Fig. 1). The isotherm expressed a big jump in high pressure
in the graph that shows that the material is microporous.
Also, it has a small hysteresis loop that shows it contains
the mesoporous materials as well. The average total pore
volume is 0.2 cm3/g and average surface area is calculated
as 32.2 m2/g.
After characterization, these catalysts were applied in the
Suzuki and Heck reaction. The Suzuki cross-coupling of
iodobenzene with phenylboronic acid was chosen as model
reaction. The optimization reaction parameters such as the
type of base and solvent, temperature and catalyst amounts
was achieved for Co-His@MNPs/Ch and given in Table S3.
In handing optimized reaction conditions, the efciency of
various prepared catalysts, as the frst used heterogeneous
cobalt catalysts in Suzuki reaction, were given in Table 1.
To illustrate merit of our study in modern organic reac-
tion, available homogenous cobalt catalyst which applied
in Suzuki cross-coupling and their reaction conditions was
added to Table 1. Clearly, our catalytic systems especially,
Co-His@MNPs/Ch are more efcient. In addition to high
efciency, our catalysts beneft from the advantages of het-
erogeneous catalysis such as easy separation and efcient
recycling.
The structure properties of all of the synthesized cata-
lysts was analyzed by X-ray diffraction pattern (XRD)
(Figures S9-S13) and compared with the MNPs/Ch (Figure
S10, a). These XRD patterns show characteristic peaks of
amorphous chitosan near the 21°θ and the appearance other
bonds which can attributed to Fe3O4 (at 2θ=30.25°, 35.75°,
43.5°, 47.85°, 53.95°, 57.05° and 63.1°) and metal Co spe-
cies (2θ=33.5°, 37.8°, 58.85° and 62.9°).
The generality and versatility of Co-His@MNPs/Ch was
examined in Suzuki reaction of aryl halides with phenylbo-
ronic acid in optimized reaction conditions. The results were
set in Table 2, a range of aryl iodides, bromides and chlo-
rides containing electron-donating and electron-withdrawing
substituents reacted efciently with phenyl-boronic acid as
more available boronic substrate and aford the desired prod-
ucts in good to excellent yields (Table 2, entries 1–17).
As can be seen, Suzuki coupling of aryl chloride was
occurred as well as aryl bromide and aryl iodide using
Co-His@MNPs/Ch catalyst. While, almost reported meth-
ods require high loadings of palladium catalyst and harsh
The cobalt content of catalysts, measured by atomic abor-
tion (AA) or inductively coupled plasma (ICP), was given in
supplemental data (Table S2). The results showed various
value for each sample, considering to applying same synthe-
sis process to fxed cobalt, comparing these results can be
used to found the best hosting ligand.
The morphology of the surfaces of some samples (Co-
MS@MNPs/Ch, Co-His@MNPs/Ch and Co-Ph@MNPs/
1 3

Pd/Cu-Free Cobalt-Catalyzed Suzuki and Heck Using Green Bio-Magnetic Hybrid and DFT-Based…
Fig. 1 TEM images and particle size distribution results for all of the synthesized catalyst
Table 1 Comparison of the catalytic activities of the catalysts studied herein with those of the reported catalysts for Suzuki reaction
Entry
Catalytic system [refs.]
Reaction conditions
Time (h)
Yield (%)
1
Co-MNPs/Ch
Co (1.6%), PEG, 80 °C
Co (2.4%), PEG, 80 °C
Co (0.22%), PEG, 80 °C
Co (1.1%), PEG, 80 °C
Co (0.7%), PEG, 80 °C
Co (1.5%), PEG, 80 °C
Without Co, PEG, 80 °C
Co (0.5 mol %), DMF, 80 °C
Co (10 mol%), THF, 60 °C
Co (0.5 mol%), CH3CN, 80 °C
Co (5 mol %), THF 60 °C
2
2
2
2
2
38
96
42
44
55
64
0
25
69
56
85
2
Co-His@MNPs/Ch
Co-MS@MNPs/Ch
Co-Ph@MNPs/Ch
Co-Cy@MNPs/Ch
Co-Sa@MNPs/Ch
His@MNPs/Ch
Co-TPy [13]
Co-SIPr.HC [14]
Cobalt-pincer complex [12]
4-pyr-(iPrPNP)CoCl [11]
3a
4
5
6
7
2
48
16
48
16
24
8a
9b
10
11c
All of the reactions (unless mentioned) occurred between bromobenzene and phenylboronic acid
aUsed iodobenzene and phenylboronic acid
bUsed the activated arylboronic pinacol esters
cUsed aryl trifate and activated arylboronic pinacol esters
1 3

A. R. Hajipour et al.
Table 2 Suzuki cross-coupling of various aryl halides in the presence of the catalyst
Entry
X
R
Yield (%)a
TON
TOF (h−1
)
1
2
3
4
5
6
7
8
I
I
I
I
3-NO2
H
2-NH2
4-OCH3
4-CN
2-NH2
3-CHO-4-OH
4-NO2
2-NO2
4-SCH3
4-COOH
4-CHO
H
97
96
91
93
96
83
88
96
97
83
95
95
94
85
84
83
69
63
40.4
40.0
37.9
38.8
40.0
34.6
36.7
40.0
40.4
43.6
39.6
39.6
39.2
35.41
35.0
34.6
28.7
26.2
20.2
20.0
18.9
19.4
20.0
17.3
18.3
20.0
20.2
17.3
19.8
39.6
19.6
17.7
17.5
17.3
14.4
13.1
Br
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
Cl
9
10
11
12
13
14
15
16
17
18
4-COCH3
4-CHO
H
2-CH2OH
4-NO2
The reaction was carried out with aryl halide (1.0 mmol), phenylboronic acid (1.1 mmol), K3PO4 (4.0 equiv.) in 3.0 mL PEG, 1 mg of catalyst at
80 °C for 2 h
aIsolated yield
conditions for Suzuki coupling reaction of aryl chlorides
with phenyl-boronic acid, anyway those catalysts display
little or no activity.
Various substituted aromatic halides underwent Heck
coupling efectively. Electron donating groups on the aryl
halides accelerated the process of conversion to products
whereas presence of electron withdrawing groups brought
about lesser conversion. Presence of iodide is preferred as
a better leaving group among the halides and aryl chlo-
rides react more slowly than other derivatives, these are
refected in the results.
From where, aryl chlorides are inexpensive and widely
available in comparison to their bromide or iodide coun-
terparts, performance a new method that active for these
derivatives is valuable.
In continues, the efciency of selected catalyst (Co-His@
MNPs/CH) was investigated in the Heck reaction. Initially,
the cross-coupling of iodobenzen with methyl acrylate was
chosen as a model.
Recycling of catalyst is an important property from
economic, environmental and industrial points of view,
the reusability of Co-His@MNPs/Ch was checked in the
model reaction. At the end of each reaction, the catalyst
was separated by an external magnetic feld, washed with
ethanol and reused. The catalyst can be reused several
times without signifcant loss of activity (Table S5). The
recovered catalyst was characterized by FT-IR, XRD,
VSM and ICP analysis, the results were illustrated in sup-
plementally data in Figures S28–S30. As can be seen, the
little changes can be seen in spectra of FT-IR XRD and
VSM in comparison with their analysis of fresh catalyst
(Figure S3, S9 and S23, respectively. The cobalt con-
tain of recovered catalyst were identifed by ICP as 0.16
The efects of the reaction conditions, such as kind of
base and solvent, temperature and amount of catalyst was
tested. The results are summarized in Table S4. As can be
seen, the best result was obtained using K3PO4 (1.5 mmol),
and 1 mg of Co-His@MNPs/Ch (2.4 mol% Co) in PEG at
45 °C (Table S6, entry 14).
Using the optimized reaction conditions, in the presented
of Co-His@MNPs/Ch, a variety of structurally diferent aryl
iodides, bromides and chlorides was applied in the reaction
with methyl acrylate to generate the desired coupling prod-
ucts (Table 3). The corresponding products was obtained in
good to high yields.
1 3

Pd/Cu-Free Cobalt-Catalyzed Suzuki and Heck Using Green Bio-Magnetic Hybrid and DFT-Based…
Table 3 Heck cross-coupling of various aryl halides in the presence of the catalyst
Entry
X
R
Yield (%)a
TOF (h−1 b
)
1
2
3
4
5
6
7
8
I
I
2-NO2
H
4-OMe
H
84
93
92
88
73
96
95
95
94
77
83
73
68
71
66
69
35.0
38.7
38.3
36.7
30.4
40.0
39.6
39.6
39.2
32.1
34.6
30.4
38.3
29.6
27.5
28.7
Br
Br
Br
Br
Br
Br
Br
Br
Cl
Cl
Cl
Cl
Cl
Cl
2-Me
4-CHO
4-CN
3-NO2
2-CHO
3-NO2
4-NO2
2-Cl
4-COCH3
4-CHO
H
9
10
11
12
13
14
15
16
2-CH2OH
The reaction was carried out with aryl halide (1.0 mmol), methyl acrylate (1.1 mmol), K3PO4 (4.0 equiv.) in 3.0 mL PEG, 1 mg of catalyst
(2.4 mol % of Co) at 40 °C for 1 h
aIsolated yield;
bNote that here TON and TOF are equivalent to each other
mmol g−1 which in comparison with fresh one (Table S2,
MNPs/Ch and Co-Sa@MNPs/Ch in the solvent (water)
have been demonstrated in Scheme 2. As can be seen Co-
His@ MNPs/Ch is just sample that in the most sable struc-
ture cobalt imprisoned on ligand section of complex. To
model the solvent, the polarized continuum model (PCM)
was used for accounting the electrostatic feld of solvent.
Scheme S1 shows all of the optimized structures for each
Co-ligand@MNPs/Ch. The calculated interaction ener-
gies for all optimized structures have been reported in
Table 4. It can be seen that the interaction energy between
Co2+ and His@MNPs/Ch in the most stable structure of
Co-His@MNPs/Ch in solvent is greater than those of the
other most stable structures related to other derivatives.
This conclusion is in agreement with the highest catalytic
efciency of Co-His@MNPs/Ch compared to the other
catalysts. Also, the natural bonding orbital calculations
were performed on the most stable structures to fnd the
natural charges of involved atoms (See Table 5). These
theoretical outcomes confrmed most stability and reus-
ability of catalyst Co-His@MNPs/Ch which found in our
experimental efort. Surprisingly, these are consonant to
its wonderful efciency. These calculating cannot justify
24.1 mmol g−1) some metal leaching was observed.
3 Computational Study
To identify the preferred interaction modes of Co species
with MNPs/Ch and its derivatives with MS, Phe, Cy, His and
Sa, the theoretical studies were performed. For simplicity,
one unit of Ch was only considered in the calculations and
the magnetic Fe3O4 nanoparticle was not included in the
calculations because it acts as a base for holding of chitosan
and its derivatives; it is same for all over.
To identify the appropriate sites of the structures for
the interaction with Co2+, the electrostatic potential map
of each structure was calculated and used for fnding the
approximate positions of Co2+ relative to the structures.
The predicted initial structures were optimized using den-
sity functional theory employing B3PW91 functional. The
SDD all pseudo efective potential was used as basis set for
all atoms. The most stable structures of Co-His@MNPs/
Ch, Co-phe@MNPs/Ch, Co-cy@MNPs/Ch, Co-MS@
1 3

A. R. Hajipour et al.
Scheme 2 The best interaction energy position for each complex
Table 4 Interaction energy
Entry Complex
A
B
C
D
E
F
(solution)
1
2
3
4
5
6
Co-MNPs/Ch
Co-His@MNPs/Ch
Co-MS@MNPs/Ch − 40.135
Co-Ph@MNPs/Ch
Co-Cy@MNPs/Ch
Co-Sa@MNPs/Ch
− 58.057* − 56.087
− 1.062 − 2.993
− 5.557 − 48.276* − 30.478
3.018
1.373
− 58.002 − 89.734*
− 30.262
− 29.486
− 0.069
− 12.225 − 42.649
− 11.011 − 14.149
− 14.077 − 68.851* − 59.303
− 50.344* − 30.238 − 43.663
− 1.675
− 63.222 − 65.337*
− 68.851
− 14.149
Table 5 The charge of Co ion in
Entry Complex
A
B
C
D
E
F
complexes
1
2
3
4
5
6
Co-MNPs/Ch
Co-His@MNPs/Ch +0.930
Co-MS@MNPs/Ch +1.744
Co-Ph@MNPs/Ch
Co-Cy@MNPs/Ch
Co-Sa@MNPs/Ch
+1.638* +1.623
+0.816 +0.899
+1.165
+1.593 +1.525*
+1.903
+1.808 +1.634* +1.901
+1.816
+1.926
+1.877
+1.874 +1.763
+1.831 +1.882
+1.874 +1.428*
+1.568* +1.898 +1.775
+1.919
1.564
+1.312 +1.315*
+1.428
catalyst operation in cobalt catalysed coupling reaction
totally, due to trusted mechanism are not reported yet. For
the moment, according to the outcomes collected we can
make the following conclusions: (I) The greater interac-
tion energy be-tween the Co2+ and coordinate atom in the
catalyst shows that the amount of the Co-His@MNPs/Ch
in the media is more than the other catalyst. (II) The more
steric congestion prevents from the appropriate approach-
ing of aryl halide and the other coupling molecule to the
Co center and decreases the rate of the coupling reaction.
(III) The amount of the positive charge on the Co center so
that the more positive charge increases the tendency of the
aryl halide for binding to Co center. The Co-His@MNPs/
Ch catalyst has the highest interaction energy, the lowest
steric congestion around the Co center and considerable
positive charge on Co center causes it is selected as the
best catalyst in this theoretical investigation which is the
agreement with the experiment.
4 Conclusion
In conclusion, we have utilized the magnetic-biopolymer
as support and several safe and available ligands to prepare
cobalt catalysts which was successfully applied for Suzuki
and Heck cross-coupling reactions. Furthermore, Co-
ligand@MNPs/Ch is a highly stable, easy handling, inex-
pensively, biodegradable support and reusable catalyst. The
1 3

Pd/Cu-Free Cobalt-Catalyzed Suzuki and Heck Using Green Bio-Magnetic Hybrid and DFT-Based…
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experimental. In addition, using the composite as a recycla-
ble catalyst in cross-coupling reactions has many advantages
including: short reaction times, high yields, low-cost and
high-throughput.
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