Design and Preparation of Poly-Selenides: Easily Fabricated and Efficient Organoselenium Materials for Heavy Metal Removing and Recycling

Article abstract of DOI:10.1002/aoc.4332

Reaction of 1,4-bis(chloromethyl)benzene with the in situ-generated NaHSe afforded a facile fabrication method of poly-selenide, a novel organoselenium material which was found to be efficient for heavy metal removing and recycling. The material could grab transition metals from their aqueous solutions and release them in HNO₃. After treating with aqueous Na₂SO₃, the polymer could be refreshed and reused. It could absorb heavier Pb even than its own weight from high concentration solutions, and remove almost all of the Pb in dilute solutions.

Full text of DOI:10.1002/aoc.4332

Received: 22 September 2017
DOI: 10.1002/aoc.4332
Revised: 25 January 2018
Accepted: 28 January 2018
F U L L P A P E R
Design and Preparation of Poly‐Selenides: Easily Fabricated
and Efficient Organoselenium Materials for Heavy Metal
Removing and Recycling
1
,2
2
2
1,2
3
1,2
Xiaobi Jing | Changzhou Chen | Xin Deng | Xu Zhang | Duo Wei | Lei Yu
1
Guangling College, Yangzhou University,
Reaction of 1,4‐bis(chloromethyl)benzene with the in situ‐generated NaHSe
afforded a facile fabrication method of poly‐selenide, a novel organoselenium
material which was found to be efficient for heavy metal removing and
recycling. The material could grab transition metals from their aqueous solu-
tions and release them in HNO . After treating with aqueous Na SO , the poly-
Yangzhou, Jiangsu 225009, China
2
Key Laboratory of Environmental
Materials and Engineering of Jiangsu
Province, School of Chemistry and
Chemical Engineering, Yangzhou
University, Yangzhou, Jiangsu 225002,
China
3
2
3
mer could be refreshed and reused. It could absorb heavier Pb even than its
own weight from high concentration solutions, and remove almost all of the
Pb in dilute solutions.
3
Testing Centre, Yangzhou University,
Yangzhou, Jiangsu 225009, China
Correspondence
Xu Zhang and Lei Yu, Guangling College,
Yangzhou University, Yangzhou, Jiangsu
KEYWORDS
environment, heavy metal removing, macromolecular, Pb, selenide
225009, China.
Email: zhangxu@yzu.edu.cn;
yulei@yzu.edu.cn
Funding information
NNSFC, Grant/Award Number: 21202141;
Opening Foundation of the Key Labora-
tory of Environmental Materials and
Engineering of Jiangsu Province, Grant/
Award Number: K14010; Yangzhou
Nature Science Foundation, Grant/Award
Number: YZ2014040; Nature Science
Foundation of Guangling College, Grant/
Award Number: ZKZD17005; Priority
Academic Program Development (PAPD);
high level talent support project of Yang-
zhou University (top‐notch talent, L. Yu)
1
| INTRODUCTION
fuctional groups outside, which could grap the metals by
[
2]
coordinations. The materials provided efficient tools to
remove and recycle the heavy metals, but the complex
structures of the materials resulted in tedious fabrication
processes and the high cost that limited the practical
applications. Thus, developing easily fabricated materials
for heavy metal recycling is still desirable in the field.
Yet, selenium chemistry has attracted chemists for a
long time, mainly because of the particular bioactivities
of the organoselenium compounds as well as their
Heavy metal pollution through industrial waste water is a
[1]
serious problem in recent years. Therefore, recycling
the heavy metals is an important research subject with
broad application scopes, not only for sewage purification,
but also for the sufficient ultilization of the resources.
During the last decade, a series of novel materials have
been developed to achieve this object. Many of them were
silica‐ or polymer‐based coating materials, with organic
Appl Organometal Chem. 2018;e4332.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4332

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JING ET AL.
[3,4]
versatile reactivities in organic synthesis.
Recently,
the green‐side of selenium began to be realized
and organoselenium‐catalyzed reactions drew much
attention for their application potential in industrial
[5–8]
productions.
During the last three years, we have
reported a variety of organoselenium‐catalyzed green
[7,8]
transformations.
Compared with transition metals,
the selenium element is eco‐safe because it is an important
and necessary trace element for human beings and can be
[5a,9,10]
metabolized in the body.
Organoselenium com-
pounds are less toxic than inorganic selenium compounds
[5d,11]
and some of them are even non‐toxic.
Moreover, sele-
nium is cheaper than noble metals and it is especially rich
1
in China. In order to accelerate the applications of these
technologies in industrial production, we began to design
and prepare the organoselenium functional materials
including the selenium‐contained polymers that might be
employed as the easily recoverable heterogeneous cata-
lysts. Recently, a facile fabrication method of poly‐sele-
nide from the accessible materials was developed and it
was unexpectedly found that despite the catalytic activi-
ties, the selenium‐contained polymer could be employed
in heavy metal recycling. Herein, we wish to report our
findings.
[8]
FIGURE 1 Photograph of poly‐selenide 3
with the peak at 431.1 having the strongest signal (See
Supporting Information). According to this result, the
macromolecular had ca 2‐5 (CH C H CH Se) units (poly
2
6
4
2
degree n = 2‐5) in average. The calculated nonintegral
poly degrees were probably caused by the unexpected sub-
stituents (e.g. Cl, OH, SeH etc) on terminal of the
macromolecular.
2
| RESULTS AND DISCUSSION
The material was initially tested in the oxidative
alkene scission reaction and ketoxime deoximation as
a heterogeneous catalyst. However, it was found to be
2
‐
First of all, since Se is a strong di‐neucleophilic reagent
and may attack the positive carbon center bearing a leav-
ing group to form C‐Se bond, it is supposed that the
less reactive than homogeneous organoselenium cata-
2
‐
[7a,b]
reacion of Se with substrates containing double leaving
lysts,
affording the ketone products in very low
groups may afford polymers, such as the poly‐selenides.
yield, while most of the substrates were not converted
In large‐scale production, heating Se powder with H
(Scheme 2, equations (3‐4)).
2
[12]
2‐
can generate H Se,
which is a Se and may condense
Fortunately, in regardless of its poor catalytic activi-
ties, the poly‐selenide 3 was unexpectedly found to be an
effective material for heavy metal removing. Recycling
experiments of Cu, Pb, Ag, Cr, Hg and Ni from their aque-
2
with diols to produce poly‐selenides free of any wastes
other than the water. But in this work, for conveniences
in laboratory operations, we prepared NaHSe (1) in situ
2
‐
as the Se synthon through the reaction of Se powder
[13]
with NaBH (Scheme 1, equation (1)).
Following reac-
4
tion of NaHSe with the commercially available 1,4‐
bis(chloromethyl)benzene (2) then led to the desired
poly‐selenide 3 smoothly (Scheme 1, equation (2)).
Poly‐selenide 3 was a water‐insoluble pale white pow-
der (Figure 1). Time‐of‐flight (TOF) mass spectrometry
analysis indicated that its weight scope was ca 400‐1000,
poly-selenide 3
O
(30 mg)
+
+
H O
2
2
Ph
Ph
(3)
Ph
Ph
EtOH (2 mL)
4
2.5 mmol
o
5
47%
8
0 C, 48 h
0.5 mmol
poly-selenide 3
30 mg)
NOH
O
(
0 o
EtOH
H2O2
C
Ph
1
Me
Ph
7
15%
Me (4)
NaBH4 + Se
NaHSe (1)
o
MeCN (2 mL), 60 C
open air, 24 h
1
, in situ
6
0.3 mmol
mmol
Cl
-[CH2C6H4CH2Se]n- (2)
NaHSe
, in situ Cl
+
1
poly-selenide 3
SCHEME 2 Test of the poly‐selenide 3 as catalyst in the oxidative
alkene scission reaction (equation (3)) and ketoxime deoximation
(equation (4))
2
SCHEME 1 Preparation of the poly‐selenide 3

JING ET AL.
3 of 6
(
Table 1). The materials were immersed into the related
TABLE 2 Recycling of Pb from aqueous solutions with different
immersing times
a
solutions at room temperature (ca 25 °C) for 36 h and
then treated with HNO to release the absorbed metals
3
Pb
Recycled
weight (mg) ratio (%)
Recycling
into another solution. The recycled metal amounts were
determined by inductively coupled plasma mass spec-
trometry (ICP‐MS). It was found that the material was
most favorable for Pb removing and 43% of the metal
could be recycled (Table 1, entries 2 vs. 1, 3‐4).
b
c
Entry (mol/L)
t (h)
d
d
d
d
1
2
3
4
0.1
24
36
48
72
37.292
74.593
78.741
82.867
18 (32, 43, 57)
36 (44, 52, 63)
38 (48, 60, 66)
40 (51, 63, 68)
Recycling experiments using a series of aqueous solu-
tions with different Pb concentrations was then con-
ducted at room temperature (Table 2). For highly
concentrated Pb solution (0.1 mol/l), the recycling ratio
reached its peak quickly within 36 h and was hardly
enhanced with extended immersing time, probably due
to the saturation of the material for Pb absorption
5
6
7
8
0.01
0.001
24
36
48
72
7.453
8.908
9.966
36
43
48
50
10.361
9
10
11
24
36
48
72
0.498
15.127
20.554
20.679
24
73
>99
>99
1
2
(Table 2, entries 2‐4 vs. 1). In the case of Table 2, entries
2‐4, the recycled Pb (74.593‐82.867 mg) was even heavier
a
Without special instruction, 50 mg of the poly‐selenide 3 was employed for
b
c
d
than the poly‐selenide's own weight (50 mg). Increasing
the polymer amount could enhance the recycling ratio
10 ml of the metal salt solution. Pb concentration. Immersing time. Values
inside the parenthesis were the recycling ratios with 100, 150 and 200 mg of
poly‐selenides, respectively.
(Table 2, entries 1‐4, see values inside the parenthesis),
but led to elevated cost of the materials. The saturation
point was delayed to 48 h for diluted solution (Pb
0
.01 mol/l), and led to the highest Pb recycling ratio at
ca. 50% (Table 2, entries 7‐8 vs. 5‐6). It was impressive that
for low concentration sample (0.001 mol/l), Pb could be
completely recycled after immersing the poly‐selenide
for 48 h (Table 2, entries 11‐12 vs. 9‐10). The material
was refreshed by soaking in aqueous Na S O (1 mol/L)
2
2 3
for 24 h and could be reused in Pb recycling experiment
again, leading to 97%, 72% and 51% recycling ratios
respectively after immersing in the dilute Pb solution
(
0.001 mol/l) for 48 h for three times of recycling
experiments.
Effect of the immersing temperature was then exam-
FIGURE 2 Recycling of Pb from aqueous solutions at different
temperature (immersing time = 48 h): (a) Pb 0.1 mol/lL; (b) Pb
0.01 mol/lL; (c) Pb 0.001 mol/lL
ined (Figure 2). Solutions with different Pb concentrations
were immersed at different temperatures and then treated
with HNO to release the metal. It was found that for all
of the samples, elevated immersing temperature resulted
in decreased Pb recycling ratio and room temperature at
ca 25 °C, as we initially employed, should be preferable
for the processes (Figure 2, curves a‐c). The experiments
conducted under ice‐water bath cooling (0 °C) also led
to decreased recycling ratios (Figure 2, curves a‐c).
3
a
TABLE 1 Recycling of the metals from aqueous solutions
Recycled
weight (mg)
Recycling
ratio (%)
b
c
d
Entry
Metal
As it has been reported that pH is an important factor
1
2
3
4
5
6
Cu
Pb
Ag
Cr
Hg
Ni
1.142
8.910
2.590
1.352
6.619
0.052
18
43
24
26
33
1
[
14]
in the adsorption processes,
the metal recycling exper-
iments were conducted in a series of solutions with differ-
ent pH values adjusted by HOAc (Figure 3). In strong
acidic solutions with pH = 2, the Pb recycling ratios fell
to 11%, 20% and 57% respectively (Figure 3, curves a‐c).
The values gradually increased and became stable in solu-
tions with pH > 3 (Figure 3, curves a‐c). The competitive
interactions of proton with the selenide moieties were
probably the reasons of the decrease of Pb recycling ratios
under acidic conditions.
a
50 mg of poly‐selenide 3 was employed for 10 mL of the aqueous metal salt
b
solution. Aqueous CuSO
4
, AgNO
3
, Pb(OAc)
2
, CrCl
2
, HgCl
2
or NiSO
4
d
(con-
c
centration: 0.01 mol/L) was employed. Determined by ICPMS. Metal
recycling ratio = recycled metal weight/metal weight in initial solution.

4
of 6
JING ET AL.
TABLE 3 Recycling Pb from aqueous solutions (Pb 0.01 mol/l)
with different Cu concentration (immersing time = 48 h, at room
a
temperature)
Recycled
Pb/mg (/%)
Recycled
Cu/mg (/%)
b
c
c
Entry
Cu (mol/l)
1
2
3
4
5
6
7
0
9.966 (48)
9.840 (47)
9.158 (44)
7.749 (37)
5.822 (28)
4.828 (23)
2.984 (14)
0 (0)
0.249 (39)
0.827 (26)
1.083 (17)
1.374 (7)
1.622 (5)
2.035 (3)
0.001
0.005
0.01
0.03
0.05
0.1
FIGURE 3 Recycling of Pb from aqueous solutions with different
pH (immersing time = 48 h, at room temperature): (a) Pb 0.1 mol/
lL; (b) Pb 0.01 mol/lL; (c) Pb 0.001 mol/lL
a
50 mg of the poly‐selenide 3 was employed for 10 ml of the metal salt solu-
tion; Pb concentration = 0.01 mol/l; immersing time = 48 h; immersing tem-
Since the in practical applications, the sewage always
contained other impurities that might affect the adsorp-
tion processes, KOAc were then employed to modified
these conditions and adjust the ionic strength of the solu-
tion. Figure 4 indicated that the Pb recycling ratios
decreased slightly after the addition of KOAc, but were
generally stable with the further increasing KOAc concen-
tration (Figure 4, curves a‐c). The results showed that the
adsorption processes were hardly affected by the
increased ionic strength caused by the soluble salts in
practical applications.
b
c
perature = room temperature. Cu concentration. Recycled metal weight
outside the bracket; recycled metal ratio inside the bracket.
Working mechanisms of the materials were proposed
in Scheme 3. Since selenium is a chalcogen element with
lone‐pair‐electron and has a strong coordination with
transition metals, the selenium moieties in poly‐selenide
3 could grab transition metals from their aqueous solu-
tions by coordination to produce the metal‐loaded poly‐
[
15]
selenide 8,
which might be oxidized into poly‐
The effect of transition metal ions was tested through
the Pb recycling experiments from the solutions with dif-
selenoxide 9 and released the metal after treating with
[
16]
oxidant such as HNO3.
The poly‐selenoxide 9 could
ferent amounts of Cu(OAc) (Table 3). Due to the occupa-
tion of the Se sites, the recycling ratio of Pb decreased with
be reduced into poly‐selenide 3 again and reused in the
next round of metal recycling experiment.
2
[
17]
the elevated Cu concentration (Table 3, entries 1‐7). Only
1
4% of Pb could be recycled from the solution with
0
.1 mol/l of Cu(OAc) (Table 3, entry 7). With the gradu-
2
-
-
[CH C H CH Se]
ally elevated Cu(OAc)2 concentration, although the
recycled Cu weight increased, the recycling ratio of Cu
decreased due to the enhanced denominator of the calcu-
lation equation (Table 3, entries 1‐7).
2 6 4 2 n
poly-selenide 3
M
[H]
M
O
-
-
-
[CH C H CH Se]
-
[CH C H CH Se]
2
6
4
2
n
2
6
4
2
n
9
8
M
[O]
[
[
[
M] = Cu, Ag, Ni, Pb etc;
O] = HNO3;
H] = Na S O
3.
2
2
FIGURE 4 Recycling of Pb from aqueous solutions with different
ionic strength (immersing time = 48 h, at room temperature): (a) Pb
SCHEME 3 Working mechanisms of the metal recycling
processes with poly‐selenide 3
0
.1 mol/lL; (b) Pb 0.01 mol/lL; (c) Pb 0.001 mol/lL

JING ET AL.
5 of 6
3
| CONCLUSION
ICPMS analysis to calculate the recycled metal amount.
Metal recycling ratio = recycled metal amount/metal
amount in original solution. After treating with aqueous
In conclusion, we have developed a facile method to fab-
ricate poly‐selenide through the direct reaction of 1,4‐
bis(chloromethyl)benzene with the in situ generated
NaHSe. The method is very convenient for laboratory
preparation and the poly‐selenide was found to be an effi-
cient material for metal recycling from the aqueous solu-
tion, especially for Pb recycling. Further investigations
on the application of this unique organoselenium mate-
rial are ongoing in our laboratory.
Na S O (1 mol/l) for 24 h, the regenerated poly‐selenide
2 2 3
could be reused in the next round of experiment.
ACKNOWLEDGEMENTS
We thank NNSFC (21202141), Priority Academic Program
Development (PAPD), the high level talent support pro-
ject of Yangzhou University (top‐notch talent, L. Yu),
Yangzhou Nature Science Foundation (YZ2014040), the
Opening Foundation of the Key Laboratory of Environ-
mental Materials and Engineering of Jiangsu Province
3
3
.1 | Experimental Procedures
.1.1 | General Methods
(
K14010) and Nature Science Foundation of Guangling
College (No. ZKZD17005) for financial support. We thank
the testing centre of Yangzhou University for assistances.
Reagents were all purchased from the merchant with
their purity more than 99%. Solvents were directly used
without special treatment. The selenium powder was
dried at 100 °C for 1 h before use. Metal contents were
determined by inductively coupled plasma mass spec-
trometry (ICPMS) on a PerkinElmer Optima 7300 DV
ICPMS device. TOF spectra were conducted on a Bruker
UHR‐TOF Maxis ultra high resolution time‐of‐flight mass
spectrometer.
ENDNOTE
1
The price of Se powder with 99.99% purity is ca $60/kg, much cheaper than
the noble metals.
ORCID
Lei Yu http://orcid.org/0000-0001-5659-7289
3
.1.2 | General Procedures for the Fabri-
REFERENCES
cation of Poly‐Selenide 3
[1] a) J. Liu, P. Wang, C. Wang, J. Qian, J. Hou, Environ. Sci. Pollut.
R. 2017, 24, 2653; b) S. Aydın‐Önen, Environ. Sci. Pollut. R. 2016,
Under ice‐water bath cooling, 0.75 g of NaBH and 1.2 g of
Se powder were added into a 50 mL round bottom flask.
4
23, 21536; (c) H. A. Naser, Mar. Pollut. Bull. 2013, 72, 6.
The flask was then charged with N and 7.5 ml of absolute
2
[
2] a) S. Guo, P. Jiao, Z. Dan, N. Duan, G. Chen, J. Zhang, Chem.
Eng. J. 2017, 317, 999; b) S. Zhang, Y. Zhang, J. Liu, Q. Xu, H.
Xiao, X. Wang, H. Xu, J. Zhou, Chem. Eng. J. 2013, 226, 30; c)
G. Dodi, D. Hritcu, G. Lisa, M. I. Popa, Chem. Eng. J. 2012,
203, 130; d) S. Lu, R. Qu, J. Forcada, Mater. Lett. 2009, 63, 770.
ethanol was injected by a syringe. The mixture was mag-
netically stirred until the black selenium powder disap-
peared (ca. 2‐3 h). Ice‐water bath was then removed and
the NaHSe solution 1 was obtained. 1 g of 1,4‐
bis(chloromethyl)benzene 2 was then injected into the
NaHSe solution by a syringe. The mixture was stirred
overnight and the grayish green poly‐selenide 3 precipi-
tated. The precipitated material was isolated by filtration
and washed by deionized water and ethanol and dried
under vacuum for 24 h to afford a pale white powder.
[
3] For selected reviews or monographs on selenium chemistry,
please see: a) T. Wirth, Organoselenium Chemistry, Vol. 208,
Springer, Berlin 2000; b) M. Birringer, S. Pilawa, L. Flohe,
Nat. Prod. Rep. 2002, 19, 693; c) T. G. Chasteen, R. Bentley,
Chem. Rev. 2003, 103, 1; d) C. W. Nogueira, G. Zeni, J. B. T.
Rocha, Chem. Rev. 2004, 104, 6255; e) G. Perin, E. J. Lenardão,
R. G. Jacob, R. B. Panatieri, Chem. Rev. 2009, 109, 1277; f) L.
Lin, J. Sheng, Z. Huang, Chem. Soc. Rev. 2011, 40, 4591; g) T.
Wirth, Organoselenium Chemistry: Synthesis and Reactions,
Wiley‐VCH, Weinheim 2011; h) B. Godoi, R. F. Schumacher,
G. Zeni, Chem. Rev. 2011, 111, 2937; i) I. P. Beletskaya, V. P.
Ananikov, Chem. Rev. 2011, 111, 1596; j) A. Nomoto, Y.
Higuchi, Y. Kobiki, A. Ogawa, Mini‐Rev. Med. Chem. 2013, 13,
3
.1.3 | General Procedures for the Metal
Recycling with Poly‐Selenide 3
5
0 mg of poly‐selenide 3 was added into 10 ml of the metal
solution (CuSO , AgNO , Pb(OAc) or NiSO ). The mix-
4
3
2
4
8
8
14; k) C. M. Weekley, H. H. Harris, Chem. Soc. Rev. 2013, 42,
870; l) Q. Li, Mini‐Rev. Med. Chem. 2013, 13, 854; m) S. T.
ture was stayed for 24‐72 h at room temperature and the
poly‐selenide was isolated by centrifugalization. The
metal‐loaded poly‐selenide was immersed in 10 ml of
Manjare, Y. Kim, D. G. Churchill, Acc. Chem. Res. 2014, 47,
985; n) S. Chaudhary, A. Umar, S. K. Mehta, Prog. Mater.
2
aqueous HNO (1 mol/l) for 24 h and then removed by
centrifugalization. The supernatant liquid was sent to
Sci. 2016, 83, 270; o) B. Banerjee, M. Koketsu, Coordin. Chem.
Rev. 2017, 339, 104.
3

6
of 6
JING ET AL.
[
4] For selected research articles, please see: a) A. M. S. Recchi, D. F.
Back, G. Zeni, J. Org. Chem. 2017, 82, 2713; b) T. Tamai, M.
Yoshikawa, S. Higashimae, A. Nomoto, A. Ogawa, J. Org.
Chem. 2016, 81, 324; c) A. A. Vieira, J. B. Azeredo, M. Godoi,
C. Santi, E. N. da Silva J., A. L. Braga, J. Org. Chem. 2015, 80,
5, 4830; i) X. Zhang, J. Ye, L. Yu, X. Shi, M. Zhang, Q. Xu, M.
Lautens, Adv. Synth. Catal. 2015, 357, 955; j) L. Yu, Y. Wu, H.
Cao, X. Zhang, X. Shi, J. Luan, T. Chen, Y. Pan, Q. Xu, Green
Chem. 2014, 16, 287; k) L. Yu, H. Li, X. Zhang, J.‐Q. Ye, J.
Liu, Q. Xu, M. Lautens, Org. Lett. 2014, 16, 1346; l) L. Yu, J.
Wang, T. Chen, Y. Wang, Q. Xu, Appl. Organomet. Chem.
2014, 28, 652; m) L. Yu, J. Wang, T. Chen, K. Ding, Y. Pan,
Chin. J. Org. Chem. 2013, 33, 1096.
2
120; d) A. C. Mantovani, T. A. C. Goulart, D. F. Back, P. H.
Menezes, G. Zeni, J. Org. Chem. 2014, 79, 10526; e) V.
Nascimento, N. L. Ferreira, R. F. S. Canto, K. L. Schott, E. P.
Waczuk, L. Sancineto, C. Santi, J. B. T. Rocha, A. L. Braga,
Eur. J. Med. Chem. 2014, 87, 131; f) L. Yu, Y. Wu, T. Chen, Y.
Pan, Q. Xu, Org. Lett. 2013, 15, 144.
[
8] Y. Wang, L. Yu, B. Zhu, L. Yu, J. Mater. Chem. A 2016, 4, 10828.
9] M. P. Rayman, Lancet 2012, 379, 1256.
[
[
10] S. Santoro, C. Santi, M. Sabatini, L. Testaferri, M. Tiecco, Adv.
Synth. Catal. 2008, 350, 2881.
[
5] For reviews, please see: a) D. M. Freudendahl, S. Santoro, S. A.
Shahzad, C. Santi, T. Wirth, Angew. Chem. 2009, 121, 8559;
Angew. Chem. Int. Ed. 2009, 48, 8409; b) C. Santi, S. Santoro,
B. Battistelli, Curr. Org. Chem. 2010, 14, 2442; c) S. Santoro, J.
B. Azeredo, V. Nascimento, L. Sancineto, A. L. Braga, C. Santi,
RSC Adv. 2014, 4, 31521; d) J. Młochowski, H. Wójtowicz‐
Młochowska, Molecules 2015, 20, 10205; e) A. Breder, S. Ortgies,
Tetrahedron Lett. 2015, 56, 2843; f) R. Guo, L. Liao, X. Zhao,
Molecules 2017, 22, 835.
[
11] F. C. Meotti, V. C. Borges, G. Zeni, J. B. T. Rocha, C. W.
Nogueira, Toxicol. Lett. 2003, 143, 9.
[12] B. E. Langner, ‘Selenium and Selenium Compounds’ in
Ullmann's Encyclopedia of Industrial Chemistry, Wiley‐VCH,
Weinheim 2005.
[
[
[
13] L. L. Lai, D. H. Reid, Synthesis 1993, 870.
14] C. H. Weng, Y. F. Pan, J. Hazard. Mater. 2007, 144, 355.
[
6] For selected recent articles, please see: a) L. Liao, R. Guo, X.
Zhao, Angew. Chem. 2017, 129, 3249; Angew. Chem. Int. Ed.
15] a) B. Manimaran, A. Vanitha, M. Karthikeyan, B. Rama-
krishna, S. M. Mobin, Organometallics 2014, 33, 465; b) F.
Saleem, G. K. Rao, A. Kumar, G. Mukherjee, A. K. Singh,
Organometallics 2013, 32, 3595.
2
017, 56, 3201; b) W.‐W. Jin, P. Zheng, W.‐T. Wong, G.‐L.
Law, Adv. Synth. Catal. 2017, 359, 1588; c) R. Guo, J. Huang,
H. Huang, X. Zhao, Org. Lett. 2016, 18, 504; d) S. Ortgies, C.
Depken, A. Breder, Org. Lett. 2016, 18, 2856; e) A. J. Cresswell,
S. T.‐C. Eey, S. E. Denmark, Nat. Chem. 2015, 7, 146; f) Z. Deng,
J. Wei, L. Liao, H. Huang, X. Zhao, Org. Lett. 2015, 17, 1834; g)
S. Ortgies, A. Breder, Org. Lett. 2015, 17, 2748; h) L. Sancineto,
C. Tidei, L. Bagnoli, F. Marini, E. J. Lenardao, C. Santi, Mole-
cules 2015, 20, 10496; i) F. Chen, C. K. Tan, Y.‐Y. Yeung,
J. Am. Chem. Soc. 2013, 135, 1232; j) J. Trenner, C. Depken, T.
Weber, A. Breder, Angew. Chem. 2013, 125, 9121; Angew. Chem.
Int. Ed. 2013, 52, 8952
[
16] A. Krief, F. Lonez, Tetrahedron Lett. 2002, 43, 6255.
[17] J. M. Khurana, V. Sharma, S. A. Chacko, Tetrahedron 2007,
63, 966.
SUPPORTING INFORMATION
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[
7] For our works on organoselenium catalysis, please see: a) T.
Wang, X. Jing, C. Chen, L. Yu, J. Org. Chem. 2017, 82, 9342;
b) X. Jing, D. Yuan, L. Yu, Adv. Synth. Catal. 2017, 359, 1194;
c) X. Jing, T. Wang, Y. Ding, L. Yu, Appl. Catal. A‐Gen. 2017,
How to cite this article: Jing X, Chen C, Deng X,
Zhang X, Wei D, Yu L. Design and Preparation of
Poly‐Selenides: Easily Fabricated and Efficient
Organoselenium Materials for Heavy Metal
5
41, 107; d) F. Wang, L. Xu, C. Sun, Q. Xu, J. Huang, L. Yu,
Chin. J. Org. Chem. 2017, 37, 2115; e) L. Yu, Z. Bai, X. Zhang,
X. Zhang, Y. Ding, Q. Xu, Catal. Sci. Technol. 2016, 6, 1804; f)
L. Yu, F. Chen, Y. Ding, ChemCatChem 2016, 8, 1033; g) X.
Zhang, J. Sun, Y. Ding, L. Yu, Org. Lett. 2015, 17, 5840; h) L.
Yu, J. Ye, X. Zhang, Y. Ding, Q. Xu, Catal. Sci. Technol. 2015,
Removing and Recycling. Appl Organometal Chem.
2018;e4332. https://doi.org/10.1002/aoc.4332