Decavanadate-based Transition Metal Hybrids as Bifunctional Catalysts for Sulfide Oxidation and C—C Bond Construction

Article abstract of DOI:10.1002/cjoc.202100145

The development of bifunctional catalysts has drawn much attention in realizing efficient and feasible catalytic systems to meet the diverse demand of potential industrial applications. Design of stable and powerful bifunctional catalysts for various cata

Full text of DOI:10.1002/cjoc.202100145

Chinese Journal
of Chemistry
CJC 中 国 化 学 - An International Journal
Accepted Article
Title: Decavanadate-based transition metal hybrids as bifunctional catalysts for
sulfide oxidation and C-C bond construction
Authors: Xianqiang Huang* Xiaoyu Gu, Yuquan Qi, Yanru Zhang, Guodong Shen*
Bingchuan Yang, Wenzeng Duan, Shuwen Gong, Zechun Xue and Yifa Chen*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2021, 39, 10.1002/cjoc.202100145.
The final Version of Record (VoR) of it with formal page numbers will soon be
published online in Early View: http://dx.doi.org/10.1002/cjoc.202100145.
ISSN 1001-604X • CN 31-1547/O6
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Huang Xianqiang (Orcid ID: 0000-0002-5063-8825)
Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Decavanadate-based transition metal hybrids as bifunctional
catalysts for sulfide oxidation and C-C bond construction
,
a
a
a
a
,a
a
a
Xianqiang Huang* Xiaoyu Gu, Yuquan Qi, Yanru Zhang, Guodong Shen* Bingchuan Yang, Wenzeng Duan,
a
a
,b
Shuwen Gong, Zechun Xue and Yifa Chen*
a
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering,
Liaocheng University, Liaocheng, 252059, Shandong, P. R. China.
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of
b
Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China.
Keywords
Decavanadate | Transition metal hybrids | Bifunctional catalysts | Oxidation of sulfides |Construction of C-C bonds
Main observation and conclusion
The development of bifunctional catalysts has drawn much attention in realizing efficient and feasible catalytic systems to meet the
diverse demand of potential industrial applications. Design of stable and powerful bifunctional catalysts for various catalysis systems is
highly desirable yet largely unmet. Here, three kinds of decavanadate-based transition metal hybrids (DTMH) (i.e. Co-DTMH, Ni-DTMH
5
and Ag-DTMH) have been successfully synthesized through a pH tuning strategy and further characterized. Specifically, the rare MO N
six-coordinated transition metal coordination modes have been detected in Co-DTMH and Ni-DTMH, while Ag atoms in Ag-DTMH
exhibited three- and five-coordinated geometries with the tuning of specially selected imidazole ligands. Thus-obtained clusters can
serve as powerful bifunctional catalysts for both sulfide oxidation and C-C bond construction. Remarkably, Ag-DTMH demonstrated
excellent heterogeneous bifunctional catalytic properties in the selective oxidation of sulfides and construction of C-C bonds (yields up
to 99%), which enable successful recycling for three cycles with remained catalytic activities and structure stability. The newly designed
decavanadate-based transition metal hybrids with bifunctional property hold high promise in the practical applications like continuous
catalysis or flow bed reactions.
Comprehensive Graphic Content
*E-mail: hxqqxh2008@163.com, chyf927821@163.com
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Chin. J. Chem. 2021, 39, XXX－XXX©
2021
SIOC,
CAS,
Shanghai,
&
WILEY-VCH
GmbH
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Chin. J. Chem. 2018, XX, 1－X

Running title
Chin. J. Chem.
[
17-18]
medicinal and biological industry.
In addition, three-
Background and Originality Content
3
component coupling of aldehydes, alkynes, and amines (A
coupling), i.e. Mannich reaction is one of powerful synthetic
processes for constructing C–C bonds in organic synthesis. Due to
its atom economy, the increasing popularity of the Mannich
reaction has been fueled by the ubiquitous nature of nitrogen-
During past decades, the numerous transition metal
coordination compounds, including polyoxotungstate (POTs),
polyoxomolybdates (POMos) and polyoxovanadate (POVs) have
attracted much attention and have found interesting applications in
diverse fields such as catalysis, sensing, energy conversion or
[19]
containing Mannich products in natural and drugs compounds.
[
1-4]
At present, although numerous efforts of the two reactions catalyzed by
POMs have been developed to overcome drawbacks associated with the
classical oxidation of sulfides and Mannich reactions, problems like
harsh reaction conditions, reusing and recycling of catalysts,
difficulty in products separation still remain concerns. To the
best of our knowledge, the reports about decavanadate-based
transition metal hybrids that serving as bifunctional catalysts in
selective oxidation of sulfides and construction of C-C bonds have
been rarely reported.
storages, etc.
POMs), can be precisely designed with tunable structural diversity
and unmatched range of structural features, sizes, and chemical
POVs, a unique subclass of polyoxometalates
(
[
5-6]
physical properties.
As an important class of POVs,
[
20]
decavanadate based POVs with well-defined structures, redox
properties and high negative charge could provide the decent
opportunities to combine with metal-organic complexes and form
the single component bimetallic POVs species with multi-
[
7-8]
functionality. Therefore, decavanadates are especially attractive
and considered to be remarkable building blocks to construct POVs-
based metal organic-inorganic hybrids.
Herein, three imidazole-decorated transition metal hybrid
decavanadate compounds [Co(1-ipIM)(H (H
DTMH), [Ni(1-ipIM)(H O) (H (Ni-DTMH), [Ag(1-
3 10 28 2 2
eIM) [Ag (1-eIM) [H V O ] ·2(1-eIM)·2H O (Ag-DTMH) have
2
O)
5
]
2
2 10 2
V O28)·6H O (Co-
]
2
2 10 2
V O28)·6H O
In this context, a series of active decavanadate-based
transition metal catalysts have been reported and exhibit multi-
2
5
2
]
2
2
4
]
2
[
9]
been successfully synthesized (Figure 1) and displayed bifunctional
catalytic properties for both oxidation of sulfides and Mannich
reaction under mild conditions. Interestingly, Ag-DTMH was more
active than Co-DTMH and Ni-DTMH, and exhibited excellent
catalytic properties (yields up to 99%). Furthermore, on the basis of
control experiments, the possible mechanisms have been proposed
to explain the observed bifunctional catalytic activity.
functionality in catalysis. For instance, An et al. presented five
decavanadate-based rare earth metal hybrids, which exhibited
highly efficient heterogeneous catalysis properties for
[
10]
cyanosilylation reactions and Knoevenagel condensations.
Naslhajian and his coworkers reported that the polyoxovanadate
NH [Zn(H O) O was found to be an efficient catalyst
(
4
)
2
2
6 2 2
] [V10O28]·4H
3
for one-pot synthesis of propargylamines by three component (A )
coupling of aldehydes, amines and alkynes without any co-catalyst
[
11]
or activator under solvent-free condition. In our previous work,
three Pd-decavanadate compounds have been successfully
synthesized and presented high activity in aerobic oxidation of
Results and Discussion
Syntheses of DTMHs
[
12]
benzylic hydrocarbons. Recently, Yang et al. reported imidazole-
decorated nickel-decavanadate POVCOFs with efficient
heterogeneous catalytic activities in the Knoevenagel
Co-DTMH, Ni-DTMH and Ag-DTMH were in situ synthesized in
aqueous solutions (wet synthesis) through the reaction of V O ,
2 5
transition metal salts and N-containing imidazole ligands (i.e. 1-
ipIM, 1-eIM). Although three different transition metal salts and
vanadium sources were applied, only protonated decavanadate
cluster is observed as the unique polyanion in these DTMHs. Based
on the previous study about the reaction conditions of
[
21]
[13]
condensation. These pioneering examples illuminates decavanadate
based materials to be highly efficient catalysts owing to the tunable
structures and existence of tremendous vanadium with redox
properties. However, despite the progress achieved, newly designed
decavanadates based crystalline materials are long-sought-after
yet still unmet.
[
22-23]
decavanadate,
different reaction conditions including mole
ratio, pH, temperature, type of precursor and base have been
optimized to find the best reaction conditions and the results
revealed the pH was investigated as the main factor for the
In general, various kinds of organic ligands including 1,4,8,11-
[
14]
[15]
tetraazacyclotetradecane
,
1,2,4-triazole
,
2-
[
16]
[12]
(aminomethyl)pyridine
and 2,2’-dipyridine amine
etc, have
been reported to synthesize the hybrid materials with
decavanadate. These ligands with diverse motifs can stabilize the
decavanadate to construct functional hybrid crystalline materials,
in which organic motifs would play the vital role in catalysis and new
catalysis units could be introduced to enrich the diversity. Among
them, imidazole derivatives (R-IM, R = -Me, -Et and -Pr, etc) are
promising organic compounds as a kind of cheap and commercially
available N-ligands, counterions, organic base and solvents and
would serve as desired chelate ligands to coordinate with other
metal sites, thus achieving bifunctional catalysts when assembly
with clusters like decavanadates. Nevertheless, imidazole-
decorated transition metal hybrid decavanadates are still rare, and
studies on these clusters with bifuctional catalytic activity are
seldom reported. In this regard, it is urgent to explore the library of
these bifunctional POVs that can serve as well-defined catalysts in
the valuable chemical transformation. In addition, it is generally
accepted that the combination of transition metal complexes and
decavanadate anions can not only expand the diversity of POVs
structure, but also possess synergistic effect on their catalytic
activities.
Figure 1 Simplified representation of the controlled syntheses of Co-DTMH,
Ni-DTMH and Ag-DTMH. Color code: Co, orange; Ni, pale blue; Ag, violent;
V, yellow; O, red; N, blue and C, gray.
The selective conversion of sulfides to sulfoxides is one of the
representative oxidation reactions and have been the focus of
chemical researchers beacuse the desired products sulfoxides are
the pivotal organic and pharmaceutical intermediates in the
Chin. J. Chem. 2021, 39, XXX－XXX
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First author et al.
formation of DTMHs. Upon tuning the pH from 6.00 to 6.87 and
optimizing the synthesis conditions, we successfully obtained Co-
DTMH as a single, homogeneous crystalline phase at a controlled
pH value of 6.54 supported by the single X-ray diffraction (SXRD)
patterns, powder X-ray diffraction (PXRD) patterns and fourier
transform infrared spectra (FT-IR) tests (Figures S1, S4). The
Ni–N and Ni–O bond distances are similar as those found in the
previous NiNO
5
model complexes [Ni(H
2 5 2
O) ] (V10O28)(1-
[
13]
pIMH) ·4H O. Besides, 3D supramolecular structure of Ni-DTMH
2 2
was further constructed by intermolecular O-H⋯O and C-H…O
hydrogen bonds (2.731–3.489 Å) (Figure 2, Table S4, SI).
conditions were as follows: V
Co(OAc) ·4H O (0.45 mmol), 1-ipIM (1.35 mmol) and 10 mL water,
5 °C for 12 h and 50 °C for another 1 h. Meanwhile, the crystal of
Ni-DTMH was achieved by replacing Co(OAc) ·4H with
Ni(OAc) ·4H O (Figures S2, S5). Besides, when AgNO was added
into the reaction to replace Co(OAc) ·4H O, it was hard to give
2 5 4 3
O (1.10 mmol), NH VO (0.63 mmol),
2
2
2
2
2
O
2
2
3
2
2
highly crystalline phase and result in unidentified powder.
Interestingly, a change of the imidazole ligand from 1-ipIM to 1-eIM
can successfully produce Ag-DTMH as proved by the SXRD, PXRD
and FT-IR tests (Figures 3, S3 and S6), indicating 1-eIM might be
more favorable for the formation of Ag-based hybrids.
Structure analyses and characterizations of M-DTMH (M = Co,
Ni and Ag)
Co-DTMH belongs to the P-1 space group and its asymmetric
units contain one-half of decavanadate anion, one
crystallographically
ipIM)(H O) } moiety and three free water molecules (Figure 1). As
presented in Figure 1, the coordination spheres of Co centers show
elongated octahedral CoNO geometries (Figure 2), in which four O
atoms of H O form the equatorial plane with the axial positions
occupied by another O atom and one N atom from 1-ipIM ligand.
The {Co(1-ipIM)(H O) } unit plays the charge balancing subunit. The
independent,
centrosymmetric
{Co(1-
2
5
Figure 2 Schematic diagram of polyhedron structure of Co-DTMH, Ni-DTMH
and Ag-DTMH. Polyhedron color code: Co, bule; Ni, pale blue; Ag, five-
coordinated, violent, three-coordinated, yellow; V, red.
5
2
Ag-DTMH was synthesized by the reaction of V
-eIM in the presence of 25% tetraethylammonium hydroxide
aqueous solution. The detailed crystallographic analysis of Ag-
2 5 3
O , AgNO and
1
2
5
lengths of the Co−N bonds are 2.083(3) Å. The Co-O terminal bond
distances are in the range of 2.102(3)-2.142(3) Å, which are similar
+
DTMH reveals that it contains two three-coordinated Ag(1-eIM)
2
2
+
cations, two five-coordinated Ag
2
(1-eIM)
4
cations, two typical
[H V O ] polyanions and two free water molecules (Figure 1). In
3 10 28
the independent Ag(1-eIM)2 ions, the Ag1 ions are three-
coordinated by two N atoms from 1-eIM ligands and one terminal
to
those
of
(Co(H
O28 polyanion, the decavanadate cluster consists
reported
Co
hybrids
3
-
[
24]
K
6
H
8
[(SeV10
O28(SeO
3
)
3
)
2
2
O)
4
)]·24H
2
O.
+
6
-
For the V10
of twenty-eight oxygen atoms and ten highly condensed VO
octahedra (Figure 2). For oxygen atoms, there are four kinds of
oxygen atoms (µ -O, µ -O, µ -O and terminal oxygen) in the
polyanion. Specifically, two µ -O oxygen atoms lie inside the
28 and are synchronized to six vanadium atoms each; four µ
O oxygen atoms lie on the surface of the decavanadate and
coordinate to three vanadium atoms each; 14 µ -O oxygen atoms
6
6
-
oxygen from V10
O
28 in a T-shape geometry, forming the Ag(1-
units (Figure 3a). Two Ag2 and two Ag3 ions act as
+
eIM)
2
6
3
2
pentadentate coordination mode and are occupied by two N atoms
6
6
-
6
−
10 28
from 1-eIM ligands, two terminal oxygen from V O and adjacent
V
10
O
3
-
2
+
Ag atom, respectively, forming the Ag
The bond distance around Ag ions are in the normal range of
.068(8)–2.125(6) Å for Ag-N bonds, 2.774(4)–2.926(4) Å for Ag-O
bonds, the bond angles of N−Ag−N, O-Ag-O and N-Ag-O are from
2
(1-eIM)
4
units (Figure 3b).
2
2
lying on the surface coordinate to two vanadium atoms each; and
eight terminal oxygen atoms lying on the outer corners synchronize
o
7
4.07(17) to 171.5(2) , which suggested the geometric
only one vanadium atom each. On the other hand, these ten VO
6
configuration of Ag atoms could be considered to be a distorted T
shape and triangular bipyram geometric coordination.
In the structure of Ag-DTMH, the decavanadate clusters are
connected by the Ag ions to give a 1D wave-like metal-organic chain
octahedra are arranged in a 3 × 2 rectangular array and connected
by sharing edges of adjacent octahedral. They are ascribed to three
different kinds of VO octahedra, that is, two octahedra without
6
terminal oxygen group lie in the center of the decavanadate cluster
and share seven edges with adjacent octahedra; four octahedra are
located at the corners of the decavanadate sharing four edges with
neighbors; and two octahedra each are at the top and bottom
sharing five edges each with neighbors.
(
Figure 3d), where two adjacent decavanadate utilize the O atoms
of terminal oxygen and bridge oxygen groups to chelate one Ag(1-
eIM) and Ag
+
2+
2
(1-eIM)
4
cations. These 1D chains are linked by the
adjacent 1D chains, free water molecules and 1-eIM ligands
through C-H⋯O and O-H…O hydrogen bonds (Table S1 and S4),
finally leading to 3D supramolecular structure (Figures 2 and 3d).
The most important structural feature is that Ag-DTMH contains
decavanadate clusters with the rare connection modes (Figure 3c).
Specifically, decavanadate acts a five bridging unit by offering five
In Co-DTMH, the decavanadate polyoxoanions and {Co(1-
2
+
ipIM)(H
2
O)
5
}
cations, free water molecules are accumulated to
form 3D supramolecular frameworks by O-H⋯O and C-H…O
hydrogen bonds (2.695-3.453 Å) (Table S4, SI) between {Co(1-
2
+
ipIM)(H
Figure 2).
The
ipIM)(H O)
2
O)
5
}
cations, the polyoxoanions and free water molecules
+
oxygen atoms to coordinate with five Ag ions (Ag1, Ag2, Ag2#1,
(
Ag3 and Ag3#2, #1 =1.5-x, 0.5+y, 1.5-z, #2 =0.5-x, 1.5+y, 1.5-z). The
ability of decavanadate clusters that acts as a bridging unit draws
silver atoms closer to each other and thus enhancing Ag…Ag
interactions. The distance between Ag2-Ag2#1 is 3.1010(13) Å,
which is shorter than the sum of the van der Waals radii of the two
crystal
structure
of
O is presented in Figure 1. The
for the structure [Ni(1-
O is made up of half a decavanadate
Ni-DTMH
[Ni(1-
2
5
]
2
2
(H
2
V
10
O
28)·6H
2
asymmetric
ipIM)(H O)
unit
V
2
5
]
(H
2
10
O
28)·6H
2
2
+
unit, one [Ni(1-ipIM)(H
2
O)
5
]
complex and three H
2
O molecules. Ni
[
25]
silver atoms (3.44 Å) , and thus the argentophilic interaction
between the silver atoms can be assumed in all cases. The strength
of the aurophilic interaction results mainly from the relativistic
cations also exhibit a NiNO
5
model (Figure 2), where six
coordination sites are occupied by the nitrogen atom of 1-ipIM
ligand, and five oxygen atoms from adjacent water molecules. The
[
26]
effects of the 5d electrons of Ag atoms.
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Running title
Chin. J. Chem.
along with a reduction in the loading catalyst to 0.5 mol% (Table 1,
entries 7-10). Nevertheless, the conversion was only 68% (entry 8)
within 1 h. Subsequently, when the reaction time was increased to
2
h, the conversion and selectivity of 99% and 94% were achieved
(entry 9), respectively. If the reaction time prolongs to 3 h, it
resulted in a decreased selectivity of 92% (entry 10). After
preliminary optimization, the optimum conditions of oxidation of
sulfides were as follows: thioanisole (0.125 mmol), hydrogen
peroxide (0.35 mmol), Ag-DTMH (0.5 mol%), MeOH (2 mL), 50 °C, 2
h. Under these conditions, the conversion and selectivity of
oxidition of thioanisole are 99% and 94%, respectively, which is
comparable
inorganic−organic hybrids [Ni(H
Table 1 The effect of different parameters on oxidition of thioanisole .
to
the
previously
O) (DTBA)
reported
POV-based
2 2
[
31]
V
2
O
4
(OH) ]·4H O.
+
2
2
2
Figure 3 (a) The three-coordinated Ag(1-eIM) unit; (b) the five-coordinated
2
a
2+
Ag
of Ag-DTMH.
2
(1-eIM)
4
unit; (c) the five bridging decavanadate unit; (d) the 1D chain
O
In order to confirm the valence of the vanadium centers in M-
DTMH (M = Co, Ni and Ag), bond valence sum calculation (BVS) was
S
Catalyst
S
H O MeOH
2
2
[
27]
carried out using the method of Brown. The BVS calculations
show that the oxidation states of V in M-DTMH are +5 (Tables S3).
Considering the charge neutrality requirement and the most
rational distribution of charges in the solid-state structures of M-
DTMH, we assume the presence of two protons attached to Co/Ni-
DTMH and three protons attached to the Ag-DTMH for charge
Entr
y
Catalyst (mol%)
t (h) Conv Sele. Reaction
b
.(%)
(%)
system
1
2
3
4
5
--
3
3
3
3
3
3
2
1
2
3
26
31
96
47
10
27
99
68
99
99
95
99
63
88
99
95
88
95
94
92
--
[
28]
Co-DTMH(1)
Ni-DTMH (1)
Ag-DTMH (1)
Homo-
Homo-
Hetero-
Homo-
Homo-
Hetero-
Hetero-
Hetero-
Hetero-
balance, as also observed in [(n-C
In generally, the FT-IR spectra can afford some valuable
5 11 4 3 3 10 3 2
H ) N] [H V O28]·2(CH ) CO.
[
29]
information for the investigation of polyoxovanadates. The FT-IR
spectra of M-DTMH (M = Co, Ni and Ag) (Figures S1-S3) exhibit the
obvious vibration bands of decenvantes clusters. The stretching
Na
AgNO
Ag-DTMH (1)
6
V
10
O
28·16H
O (1)c
2
−
1
−1
bands of V = O
t
in Co-DTMH appear at 948 cm , 947 cm for Ni-
6
7d
8d
9d
3
(1)
−
1
DTMH and 951 cm for Ag-DTMH, respectively. Absorption bands
at 838, 747 and 586 cm for Co-DTMH (Figure S1), 834, 747 and
86 cm for Ni-DTMH and 829, 749 and 594 cm for Ag-DTMH,
−
1
−
1
−1
Ag-DTMH (0.5)
Ag-DTMH (0.5)
Ag-DTMH (0.5)
5
respectively, (Figures S2-S3) can be ascribed to the V–O–V
stretching vibrations. The vibrational signals in the region of 1086-
0d
1
−
1
1
635 cm region are attributed to the vibration of v(C=C) and
a
v(C=N) of organic imidazole ligands in M-DTMH (M = Co, Ni and
Reaction conditions: thioanisole (0.125 mmol), H
2
O
2
(0.35 mmol) and
Ag). Besides, the broad peaks at 3109-3430 cm−1 originated from
[
30]
b
c
catalyst in MeOH (2 mL), 40 °C. The by-product detected is sulfone.
O was prepared using a literature method. [32] Reaction
d
the stretching vibration ν(O−H) of H
2
O or ν(N−H) of protonated
Na
V
6 10
O
28·16H
2
organic ligand.
temperature, 50 °C; Homo-: Homogeneous; Hetero-: Heterogeneous.
In order to investigate the purity of the three M-DTMH (M =
Co, Ni and Ag), the crystal samples were grinded to obtain suitable
powder and characterized by PXRD test. As shown in Figures S4-S6,
the PXRD patterns of M-DTMHs (M = Co, Ni and Ag) were in well
agreement with those of as synthesized one, which revealed the
high phase purity of obtained samples.
To verify the catalytic activities of each component in Ag-
6
-
DTMH, AgNO
studied to investigate in the oxidation of thioanisole to sulfoxide.
When using AgNO as the catalyst under optimum conditions a
conversion of 27% and a selectivity of 95% were achieved. The
conversion was 10% when Na O was utilized as the
single catalyst. These above results reveal that the combination of
3
and corresponding V10O28 have been further
3
6 10 2
V O28·16H
Selective oxidation of sulfides
+
6-
Ag and V10
O
28
would possess synergistic effect on the
Here, the catalytic activities of M-DTMH (M = Co, Ni and Ag)
for oxidizing sulfides were investigated in detail. Initially, the
oxidation of thioanisole as the model reaction was established to
investigate the catalytic performance of M-DTMH (M = Co, Ni and
enhancement of both conversion and selectivity for the oxidation
of thioanisole, which is in accordance with the previously reported
findings of the transition metal cations and polyoxoanion units
[33]
based catalsyts.
Ag) in MeOH using H
showed that the reaction achieved only 26% conversion in the
absence of the catalyst (Table 1, entry 1). Next, thioanisole and H
2 2
O as green oxidant. The blank experiment
On the basis of optimum of selective oxidation of thioanisole,
several substituted thioanisole derivatives with electron-donor and
withdrawing groups, steric group were evaluated. As shown in
Table 2, various substituted thioanisoles were scanned (-Cl, -Br, -
NO ). The introduction of the electron donor and withdrawing
2
O
2
-
along with the M-DTMH were mixed uniformly with methanol in a
Schlenk tube and reacted at 40 °C for 3 h, achieving the desired
product (methylsulfinyl)benzene (conv. 31-96%, sele. 63-99%, Table
2
groups to thioanisole results in a slight decrease of the conversion
in comparison with that of thioanisole. However, the oxdition of p-
bromo- or nitro- substituted thioanisoles lead to the poor
selectivity for target products (Table 2, entries 4-5). In addition, it
seems that the steric hindrance of the substrate also possesses a
slight influence on the selectivity of sulfide to sulfoxide when
compared with p-chlorothioanisole and o-chlorothioanisole (Table
1
, entries 2-4). Significantly, it was found that Ag-DTMH was
insoluble in the reaction and exhibited heterogeneous catalytic
behavior; whereas, Co-DTMH and Ni-DTMH were soluble in the
MeOH and difficult to be recycled. Thus, the heterogeneous
catalytic efficiencies of Ag-DTMH were assessed by changes in the
reaction conditions, including temperature, loading catalyst, and
reaction time. The catalytic results revealed that temperature of
2
, entries 3 and 6).
5
0 °C led to a high conversion of 99% but only 88% for the selectivity
of obtained product. The selectivity was further increased to 95%
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Table 2 Substrate scope for oxidation of sulfidesa.
The results revealed that Ag-DTMH could be reused for at least
three runs [Conversions: 99% (first run), 97% (second run), 98%
(third run)] with negligible decay in activity (Figure 4a). Besides, the
recovered Ag-DTMH presented remained structural integrity as
proved by XPS, FT-IR and PXRD tests, implying high structure
stability during the recycling tests (Figures 4b-d).
O
S
S
Catalyst
R
R
H O MeOH
2
2
According to the previous studies about sulfoxidation and the
above experiment results, peroxo-metal intermediate generally
played an important role in the catalytic oxidation of sulfoxidation
Entr
y
Substrates
Products
Conv.(%)
Sele.(%)b
[
34]
when using H
of peroxovanadium species was observed by the Raman spectra of
the H -treating Ag-DTMH during the sulfoxidation (Figure S27),
2 2
O as the green oxidant. Specially, the O-O stretch
O
S
S
2 2
O
99
94
[35]
which is agreement with the reported results. Thus, we proposed
a possible reaction path of oxidation of thioanisole in Figure S28. In
1
2
2 2
the possible pathway, Ag-DTMH firstly interacted with H O to form
O
S
S
active peroxovanadium species, which would facilitate the
oxidation reaction with the S atom of thioanisole and generate the
corresponding oxidation products.
H
CO
99
99
99
78
78
52
3
H
3
CO
Mannich reaction
O
S
S
Based on the interesting results of oxidation of sulfides, we
further verify our idea via Mannich reaction for constructing C-C
bonds. In this context, there are two active components in these
DTMHs (i.e. transition metal and decavanadate cluster). As we
know, transition metals like Ag generally can catalyze the
3
4
Cl
Br
Cl
O
S
S
multicomponent reactions, especially that coupling of the alkynes
[36]
Br
with three-component reactions.
Consequently, there is
considerable interest from the synthetic point of view to obtain the
propargylamines by novel efficient methodologies. Therefore, we
have explored the catalytic efficiency of the Ag-DTMH in C-C
coupling of aldehydes, alkynes and amines at 40 °C.
O
S
S
5c
99
95
66
99
O2N
O N
2
Table 3 The effect of different parameters on Mannich reactiona.
Cl
Cl
O
S
6c
S
H
N
N
Catalysts
HCHO, MeCN
a
Reaction conditions: sulfides (0.125 mmol), H
2
O
2
(0.35 mmol), catalyst (0.5
Conv.(
%)
Yields
(%)b
Entry
Catalyst (mol%)
t (h)
mol%), MeOH (2 mL), 50 °C, 2 h. b The by-product detected is sulfones.
c
60 °C, 4 h.
1
2
3
4
5
6
7
8
9c
Co-DTMH (1)
Ni-DTMH (1)
Ag-DTMH (1)
4
trace
8
trace
8
4
4
37
36
AgNO
3
(1)
4
32
31
Na
6
V
10
O
28·16H
2
O
4
trace
0
trace
--
--
4
Ag-DTMH (1.5)
Ag-DTMH (2.5)
Ag-DTMH (0.5)
Ag-DTMH (0.5)
12
12
1
64
64
81
80
78
77
1 c
0
2
99
99
aThe reactions were carried out using phenylacetylene (0.25 mmol),
piperidine (0.5 mmol), formaldehyde (0.5 mmol), and catalyst in MeCN (1
b
c
mL), 25°C. The yields are detected by GC. Reaction temperature, 40 °C.
Before optimizing the one-pot sequence of this
transformation, initial studies were devoted to finding the best
conditions for the construction of propargylamines. At first,
phenylacetylene, piperidine and formaldehyde were selected as
the model substrates to investigate the catalytic performance of M-
DTMH (Table 3). Three component coupling conditions using M-
DTMH as the catalyst in 1 mL acetonitrile led to the desired 1-(3-
phenylprop-2-yn-1-yl)piperidine with a relatively low yield (Table 3,
entries 1-3). It is noteworthy that the yield of desired product
catalyzed by Ag-DTMH is higher than those of Co-DTMH and Ni-
Figure 4 (a) The results of oxidition of thioanisole catalyzed by Ag-DTMH in
three runs reused experiments. (b) The XPS of Ag in Ag-DTMH before and
after three runs reaction. (c) The IR of Ag-DTMH before and after three runs
reaction. (d) The PXRD patterns of Ag-DTMH before and after recycling tests.
Additionally, the reutilization and stability of the Ag-DTMH was
further investigated in the sulfoxidation under optimum conditions.
Ag-DTMH was filtered from the reaction mixture after reaction and
then washed by methanol and reused for the oxidation of sulfides.
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Running title
Chin. J. Chem.
DTMH. Besides, the high catalytic efficiencies of Ag-DTMH were
efficiently, affording the coupling products in high yields (99%). The
Ag-DTMH system successfully catalyzes the coupling of substituted
phenylacetylene using substrates with electron-rich, and -deficient
functional groups (Table 4, entries 2-5). In addition, this
transformation tolerates the coupling of steric hindrance o-
chlorophenylacetylene (Table 4, entry 6), affording the
corresponding products in similar yield as that of entry 1. Notably,
higher yields could also be achieved when pyrrolidine and
morpholine were presented in the Mannich reaction (Table 4,
entries 7-8). In addition, Ag-DTMH exhibits remained structure and
activity during the cycling tests, indicating high stability of Ag-DTMH
in catalyzing Mannich reaction (see Figures S29-S30).
[
37]
comparable to already reported POMs.
Therefore, Ag-DTMH
with the best performance is selected as the target catalysis model
for further characterization.
To evaluate the catalytic performance of each component of
Ag-DTMH on the Mannich reaction, a series of controllable
experiments were carried out. The blank experiment indicated that
only trace conversion was achieved in the absence of catalysts
(
Table 3, entry 5). The reaction with AgNO
homogeneous system and exhibited a product yield of 31% (Table
, entry 4). Those control experiments obviously suggested that the
3
as the catalyst was a
3
combination of Ag cation and POVs, that was, Ag-DTMH played an
important role in the Mannich reaction. Next, changing the reaction
time and the amount of catalyst, such as 12 h, 2.5 mol% catalyst,
led to a dramatic increase of the yields (Table 3, entries 7-8).
Subsequently, we turned our attention to change the reaction
temperature from 25 °C to 40 °C with reaction time of 1 h, and a
significant improvement in the yield (77%) was observed (Table 3,
entry 9). When the reaction time was increased to 2 h, the product
was achieved in a 99% yield (Table 3, entry 10). Consequently, the
best conditions for the 1-(3-phenylprop-2-yn-1-yl)piperidine were
optimized as follows: phenylacetylene (0.25 mmol), piperidine (0.5
mmol), formaldehyde (0.5 mmol) and Ag-DTMH (0.5 mol%), MeCN
On the basis of previous literature reports and above experimental
results, a tentative plausible catalytic mechanism catalyzed by Ag-
[38-40]
DTMH is depicted in Figure S31.
Initially, Ag-DTMH interacts with
the triple bond of the phenylacetylene to produce intermediate B.
Furthermore, B transforms into Ag-acetylide intermediate C under the
[41]
reaction conditions . Next, Ag-acetylide C reactes with imnium ion
obtained from the condensation reaction of aldehyde and amine to
furnish the corresponding propargylamine. Finally, the catalyst is
regenerated at the end of the cycle for a new sequence of reaction.
Conclusions
(1 mL), 40 °C, 2 h.
In summary, three M-DTMH (M = Co, Ni and Ag) catalysts have
been successfully prepared through the assembly of imidazole
based ligands and decavanadate cluster through a pH tuning
strategy. The selection of various transition metals and imidazole
based ligands resulted in powerful catalysts with tunable structures
and multi-functionality. Notably, one of them, Ag-DTMH exhibited
excellent bifunctional catalytic properties in both the selective
oxidation of sulfides and the three-component coupling reaction.
Besides, Ag-DTMH can be well recycled with maintained inert
structures and catalysis activity. These powerful catalysts with the
specially designed multi-functionality inheriting from the
combination of transition metals and decavanadate cluster would
pave a new way in the exploration of POM-based catalysts in multi-
functional catalysis.
Table 4 Substrate scope for Mannich reactiona.
N
Catalyst
HN
n
X
X
HCHO, MeCN
n
R
R
X=C, O; n =1, 2
En
Conv. Yields
Substrates
Products
(%) b
try
(%)
N
99
99
99
99
99
99
99
99
99
1
2
Me
N
N
99
99
99
99
99
99
99
Me
Experimental
Et
Materials and instruments
3
4
5
6
7
8
Et
All chemicals and solvents in this study were reagent grade
and used as received from commercial sources without further
purification.
n-Pr
N
n-Pr
IR spectra of M-DTMHs were measured on Nicolet 170 SXFT/IR
−
1
Cl
spectrometer through KBr pellet in the range of 4000−400 cm
N
region. Powder X-ray diffraction (PXRD) patterns were recorded on
a Rigaku D/max-2550 diffractometer with Cu Kα radiation. GC
analyses were performed on Shimadzu GC-2014C with a flame
ionization detector equipped with a 30 m column with nitrogen as
carrier gas. After the each catalytic reaction was completed, the
result of product was evaluated by GC-MS (Agilent 7890A-5975C).
Cl
Cl
N
Cl
N
O
Syntheses of M-DTMHs (M = Co, Ni and Ag)
2 5 4 3
Synthesis of Co-DTMH: V O (1.10 mmol, 200 mg) and NH VO
(0.63 mmol, 73.9 mg) were slowly added to 10 mL water in turn.
After the solution was stirred intensely for 60 min at 25 °C,
Co(OAc) ·4H O (0.45 mmol, 112 mg), 1-ipIM (1.35 mmol, 155 μL)
2 2
were added. The solution were continuously stirred for 30 min, and
N
aReaction conditions: arylacetylenes (0.25 mmol), cyclic secondary amines
(
4
0.5 mmol), formaldehyde (0.5 mmol), catalyst (0.5 mol%), MeCN (1 mL),
0 °C, 2 h. The yields are detected by GC.
b
a 1 M CH COOH solution was used to adjust the pH value of the
3
solution to 6.54. The reaction mixture of earthy yellow was stirred
for another 12 h and followed to heat at 50 °C for 60 min. Finally,
the resulting mixture was filtrated and the resulted filtrate stood for
two weeks, orange crystals Co-DTMH, suitable for X-ray diffraction,
were obtained. Yield: 60.8%. Anal. calcd. (%) (found) for
With the optimized conditions in hand, the generality of this
sequential one-pot reaction was examined using a series of
substituted phenylacetylene derivatives and the corresponding
results were shown in Table 4. Gratifyingly, the reaction works
Chin. J. Chem. 2021, 39, XXX－XXX
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First author et al.
C
7
12
H
54Co
2
N
4
O
44
V
10: C, 9.28 (9.09); H, 3.42 (3.43); N, 3.44 (3.53); Co,
ionization detector and the qualitative result of product was
evaluated by GC-MS (Figures S19-S26).
-
1
.37 (7.43); V, 30.96 (31.12). FT-IR spectrum, ν (cm ): 3400 (s), 1635
(s), 1517 (w), 1420 (s), 1312 (w), 1244 (w), 1118 (w), 1094 (w), 947
s), 838 (s), 746(s), 586 (s), 462 (w).
(
Supporting Information
Synthesis of Ni-DTMH: The synthesis method of Ni-DTMH was
similar to that of Co-DTMH except that Ni(OAc)
19 mg) was used instead of Co(OAc) ·4H O (0.45 mmol, 112 mg),
and the pH value was adjusted to 6.00 by 1 M CH COOH. Yellow
crystals of Ni-DTMH were harvested after two weeks of growth.
Yield: 57.4%. Anal. calcd. (%) (found) for C12 Ni 10: C, 9.34
9.19); H, 3.39 (3.43); N, 3.49 (3.53); Ni, 7.44 (7.40); V, 31.36 (31.23).
2 2
·4H O (0.45 mmol,
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
1
2
2
3
Acknowledgement (optional)
H
54
N
4
2 44
O V
(
-
1
The work was financially supported by the National Natural
Science Foundation of China (No. 21871125 and 21901122); the
Natural Science Foundation of Shandong Province, China (No.
ZR2019MB043and ZR2019QB022); the Construction Project of
Quality Curriculum for Postgraduate Education of Shandong
Province (No. SDYKC19057) and the Natural Science Research of
Jiangsu Higher Education Institutions of China (No. 19KJB150011)
and Project funded by China Postdoctoral Science Foundation (No.
2019M651873).
FT-IR spectrum, ν (cm ): 3396 (s), 1632 (s), 1515 (w), 1420 (s), 1338
(
(
w), 1311 (w), 1265 (w), 1242 (w), 1116 (w), 1092 (w), 946 (s), 833
s), 747 (s), 585 (s), 458 (w).
2 5
Synthesis of Ag-DTMH: V O (1.10 mmol, 200 mg) and 25%
tetraethylammonium hydroxide (1.11 mmol, 160 μL) were slowly
added to 15 mL water in a clean beaker. The above solution was
stirred intensely at 35 °C for 60 min, and to this were added AgNO
3
(0.59 mmol, 100 mg), 1-eIM (1.87 mmol, 180 μL). The solution were
3
continuously stirred for 30 min, and 1 M HNO solution was used to
adjust the pH value of the solution to 6.87. The reaction mixture of
earthy yellow was stirred for another 10 h and followed to heat at
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Running title
Chin. J. Chem.
Entry for the Table of Contents
Decavanadate-based transition metal hybrids for bifunctional sulfide oxidation and C-C bond construction
Xianqiang Huang*, Xiaoyu Gu, Yuquan Qi, Yanru Zhang, Guodong Shen*, Bingchuan Yang, Wenzeng Duan, SHuwen Gong, Zechun Xue and Yifa Chen*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Three decavanadate-based transition metal hybrids have been successfully synthesized and the decavanadate-based Ag-DTMH demonstrated excellent
heterogeneous bifunctional catalytic properties in the selective oxidation of sulfides and construction of C-C bonds (yields up to 99%)
Chin. J. Chem. 2021, 39, XXX－XXX
© 2021 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
www.cjc.wiley-vch.de