Polyoxomolybdate-stabilized Cu2O nanoparticles as an efficient catalyst for the azide-alkyne cycloaddition

Article abstract of DOI:10.1039/c6nj00868b

We report a simple methodology for the stabilization of Cu₂O nanoparticles of size 10-30 nm on the polar pore surface of the polyoxomolybdate (NH₄)₁₂[Mo₃₆(NO)₄O₁₀₈(H₂O)₁₆] ({Mo₃₆}). For the first time, a Cu₂O@{Mo₃₆} composite has been utilized as a recyclable catalyst for the Huisgen 1,3-dipolar cycloaddition reaction of terminal alkynes, aryl/alkyl halides and NaN₃ for the synthesis of 1,2,3-triazoles.

Full text of DOI:10.1039/c6nj00868b

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Polyoxomolybdate-stabilized Cu2O nanoparticles as an efficient catalyst
for the azide–alkyne cycloaddition
Mojtaba Amini,* a Hadi Naslhajian, a,b S. Morteza F. Farnia,*b Hee Kyoung Kang,c Sanjeev Gautamd and Keun
Hwa Chae*c
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
We report a simple methodology for the stabilization of Cu2O nanoparticles of size 10–30 nm on the polar pore surface of a
polyoxomolybdate(NH4)12[Mo36(NO)4O108(H2O)16] ({Mo36}). For the first time, a Cu2O@ ({Mo36} composite has been utilized as a
10 recyclable catalyst for the Huisgen 1,3ꢀdipolar cycloaddition reaction of terminal alkynes,aryl/alkyl halidesand NaN3 for the synthesis of
1,2,3ꢀtriazoles.
50 [36], we could also address its stabilizing effect on Cu2O
nanoparticles. The {Mo36} polyoxomolybdate skeleton acts as a
localized support that gives rise to highly dispersed and stabilized
Cu2O nanoparticles (Scheme 1). Also, a simple, green, and
55 oscfa1la,b2l,3eꢀtprrioazcoeslesspfrroocmessarfyolr/aolknyel–hpaolitdmesu,ltailckoymnepso,naenndt sNynatNh3esiins
water, which are catalyzed by polyoxomolybdateꢀstabilized
Cu2O nanoparticles is herein reported.
Introduction
15 dTihreec1t ,r3oꢀudtiepotloar1c,2y,c3lꢀotaridadziotiloesn, ohfasorignaanrgicuaabzliydebsecaonmdealtkhyenemso, sat
popular ligation reaction that has been widely applied in many
areas such as polymers, drug discovery, and advanced material
science, etc [1ꢀ5]. Early work has been focused on the
20 dmeuvletilcoopmmpeonnt enotf ccooppppeerrꢀ(cI)ataclaytzaelydtaizcidsey−steamlksynfeor cythceloaodndeiꢀtipoont
(CuAAC) reaction [6ꢀ10]. Cu2O is also a source of catalytic Cu(I)
for these reactions, but direct use of Cu2O powder in a CuAAC
reaction usually requires long reaction times and yet result in
In order to
25 ionvceormcopmleetethcoesnevedrrsaiownbaacnkds, speovoerrayliereldsesar[c1h1ꢀg1r3o]u.ps have made
enormous efforts to enhance the catalytic efficiency of Cu2O [14ꢀ
18]. The most common method employed for the synthesis of
Cu2O nanoparticles is the reduction of metal ions in the presence
or hydrazine as a reducing agent, which are quite
30 oexfpNenasBivHe and possible hazard to the environment [19ꢀ21].
4
Polyoxometalates (POMs) are wellꢀdefined metal– oxygen cluster
anions that can be characterized by their ability to undergo
stepwise, multielectron redox reactions, whilst their structure
Scheme 1. General procedure for the synthesis ofCu2O@{Mo36}
35 trheemaeilnecstrinotsatacttic[2a2dꢀs2o5r]p. tTiohne ohfigmheatanlioinoincscohnarPgOe MofsPsOurMfasceca[u2s6e]s.
Then POMs can participate in catalytic redox processes as
electron relays. Therefore, reduction potentials of POMs make
them ideal candidates for the stabilization of nanoparticles [27ꢀ
60
Experimental
40 3p0ar]t.icTlheis isagatgtrreibguatteiodnto thbeyir hieglhecatnrioosntaicticcharrgeep,uwlshiiocnh. preGveianntst
polyoxomolybdate clusters, aside from interest in their enormous
structural diversity, are of special importance in this context as
they may provide highly symmetric, rigid, nanometerꢀsized
inorganic framework molecules [31ꢀ35].
Material
Chemicals and solvents were purchased from the Fluka and
Chemical companies. (NH4)12[Mo36(NO)4O108(H2O)16]
65 M({Mercok36}) was prepared according to our previous procedure [36].
Preparation of Cu2O@{Mo36}
Polyoxomolybdate (NH4)12[Mo36(NO)4O108(H2O)16] (0.01 mmol)
45 Herein, we report an alternative, versatile and greenꢀchemistry
procedure for the stabilization of Cu2O nanoparticles on POMs,
as a support as well as a reducing agent. By controlling the
experimental conditions so as to retain a polyoxometalate
structure, specifically, (NH4)12[Mo36(NO)4O108(H2O)16] ({Mo36})
70 mwamsoslu)swpeansdaedddeindeftohlylolwaceedtabtye s(t1i0rrimngL)atanrodotmhetnemcoppepraetrurneitfroarte2(14
h. During stirring the color of solids was changed to green and
then yellow orange which shown the direct reduction of Cu(II) to
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Cu(I) species. The solid was filtered off, washed with ethyl
acetate and finally with diethyl ether and dried in air.
5 AGleknyenreal(p0r.5omcemdoulr)e, ftohrethoergaazniidce–haallkidyene(0c.y5c5lmoamdodli)t,ioannd NaN3
(0.55mmol) were added to a solution of Cu2O@{Mo36} (5 mol%)
in H2O (2mL). The reaction mixture was warmed to 70 °C and
monitored by TLC until total conversion of the starting materials.
10 Wextartaecrti(o3nmwLit)h wEatOs Aadcd(e2d×t1o0tmheLr)e. sTuhlteincgolmleicxtetudreo,rgfoanlliocwpehdasbeys
were dried with anhydrous CaCl2 and the solvent was removed in
vaccum to give the corresponding triazoles, which did not require
any further purification.
15 Results and Discussion
Preparation of Cu2O@{Mo36}
Polyoxomolybdate
(NH4)12[Mo36(NO)4O108(H2O)16]
was
suspended in the ethyl acetate solution of copper nitrate,
20 rfoellalotiwveeldy byeyllsotwirroinragnagtercooolmoretdemCup2eOra@tu{reMfoo3r6}2. 4 h to obtain a
Catalyst characterization
To gain insight into the structure of Cu2O@{Mo36} catalytic
25 Xsy-srtaeym, awnealyhsaivse(EchDaXra)c,terXizꢀeradythedicfafrtaaclytisotnby(XenReDrg)y, disscpaenrnsiinvge
electron microscopy (SEM) and transmission electron
microscopy (TEM). XRD patterns of {Mo36} and Cu2O@{Mo36}
were quite similar (Fig. S1).The morphology and size of the
30 TCEuMO aNnPdsHsRtaTbEiliMzedanidn rtehper{esMenotat}ivmeaitmriaxgweseraerestsuhdoiwednbiny FSiEgM. 1,
and Fig. 2 respectively. The TEM images show homogeneous
distribution of dark Cu2O NPs with size 10–30 nm throughout the
POM matrix (Fig. 2b). Furthermore, the selected area electron
2
36
35 rdiinffgrꢀalciktieonp(aStAteErnDs) piantdteerxnesdfrotom athlearg(e1r1s1a)m, pl(e20a0re)a sahnodwe(d22th0e)
reflections, suggesting the presence of cubicꢀphase Cu2O on the
{Mo36}. It is worth noting that the solution impregnation method
enables incorporation of metal salts into the pores of the POM
40 meleactrtirxo,stwathicereintthereayctiinotnesra. cTthweitlhoapdoinlagr ofufnCctui2oOnailngtrhoeupssurtfharcoeugohf
catalyst is determined by EDX analysis, and is found to be 4.37%
(Fig. S2).
50 Fofig.C2u2TOE@M{Mimoa36g}es of a) {Mo }; b) Cu O@{Mo }; c) HRTEM images
36
2
36
To confirm the direct reduction of Cu(II) to Cu(I) species on the
POM, the chemical state of the Cu on the surface was analyzed
55 lbeyveXl ꢀsrpaeyctpruhmotosehloewctsrotnwospienctternossecoppeyak(sXaPtS9).32T.2heanCdu925p2.1coerVeꢀ,
which can be assigned to Cu 2p3/2 and Cu 2p1/2 spin−orbital
components of Cu(I) specials, respectively [37], whereas the
satellite peaks associated with Cu(II) species at 934.6 are rather
60 {wMeaok3,6}prsouvrfiancget[h3a8t].CTuhOe Cwua2sOre/dCuucOedrattoiofboyrmcoCmupaOrindgirethcetlyratbioy
2
of satellite to main peaks intensities of Cu 2p3/2 in XPS spectra
are estimated to be about 1.82.
45 Fig. 1 SEM images of a) {Mo36} b) Cu2O@{Mo36}
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not have any appreciable influence on the outcome of the reaction
(entries 1–6). Furthermore, steric hindrance due to the ortho
substituents on the benzyl chloride affected the reaction progress
45 aonrtdhothpeorseiftoioren wbeanszlyelsschreloacritdiveestuobtshtietuctyecdlowaditdhitimonethreyalctgiroonutphaant
the para derivative (entries 2 and 3). When benzyl bromide was
used under the similar reaction conditions, the corresponding
products were obtained in higher yields than the case of benzyl
50 chloride (entries 7ꢀ9).
Table 2. Cycloaddition of benzyl halides with terminal alkynes in the
presence of Cu2O@{Mo36}
R1
R1
Fig. 3 Cu 2p XPS peaks of Cu2O@{Mo36}
R2
N
N
2
R3
X
+
NaN3
+
N
0
H2O, 70 C
R2
R3
5
Catalytic effects
The presence of highly monoꢀdispersed Cu2O NPs with uniform
size on the POM matrix prompted us to study its catalytic activity
for Huisgen 1,3ꢀdipolar cycloaddition reactions. Initial reactions
Entry
1
2
3
4
5
6
7
8
R1
Ph
4ꢀMeꢀPh
2ꢀMeꢀPh
4ꢀNO2ꢀPh
R2
X
R3
Ph
Ph
Ph
Ph
Yield (%)
H
H
H
H
H
H
H
H
H
Ph
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
Br
Br
88
82
73
90
86
85
95
91
93
64
10 twheeremcoadrreiledsuobusttrbaetetws,eeans bshenozwynl cihnloTraidbelew1it.hIpnhethniyslapcreetlyimleinnearays
experiment, the Huisgen cycloaddition reaction was carried out in
various solvents, with Cu2O@{Mo36} as a catalyst, in air at 70 °C
for 12 h. The reaction proceeded perfectly in water (entry 3), but
15 syoielvldesntsdec(erenatsrieeds w4h–e8n). thOen retahcetioonthewrashacnadrr,iebdlaonukt icnataoltyhteicr
reactions without catalyst or in the presence of {Mo36} showed no
conversion, suggesting the role of Cu2O nanoparticles in
catalyzing click reactions (entries 1, 2). Considering to develop
Ph
Ph
Ph
Ph
Ph
Ph
4ꢀMeOꢀPh
4ꢀMeꢀPh
Ph
4ꢀMeOꢀPh
4ꢀMeꢀPh
Ph
9
10
20 wanateecroansoma icgareleanndsoelvnevnirtoinsmcelnetaarlllyy tfhreienmdolyst rfeaavcotiroanb,leucsiansge oinf
these reactions. As indicated in Table 1, the reaction did not
initiate at room temperature under conventional stirring using a
magnetic stirrer for 12 h (entry 9), but a significant growth
25 (inencrtreiaesse1i0nꢀt1h2e).prAoldsuoctthyeieCldu(wIIa)sꢀcoabtasleyrzveedd[a3t+h2i]ghceyrcltoeamdpdeirtiaotunreosf
phenylacetylene and benzyl azide in water with 5mol% of
Cu2O@{Mo36} resulted in 97% of 1ꢀbenzylꢀ4ꢀphenylꢀ1,2,3ꢀ
traizole.
55 Repeated use of a catalyst is an important parameter in its
evaluation, the reusability of the catalyst Cu2O@{Mo36} system
was investigated. After precipitation and filtration of the azide–
alkyne cycloaddition products, water solution of the catalyst was
60 wreeurseedcafrorriendewoutcywciltehorfeltahteivreelaycthiiognh. Tyiwelodr(eFciygc.li4n)g. Semxpaellrilmoessnetss
of catalyst mass during washing procedure may be caused in the
low diminution in the activity from the first to the third cycle.
30 Table 1.The Effect of various conditions on the azide–alkyne
cycloaddition
Entry
catalyst
Temperature
solvent
Yield
(%)
0
(°C)
70
70
70
70
70
70
70
70
r.t.
40
50
60
1
2
3
4
5
6
7
8
9
ꢀ
H2O
H2O
H2O
C2H5OH
CH3CN
toluene
C6H6
EtOAc
H2O
{Mo36}
0
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
Cu2O@{Mo36}
88
51
38
11
7
15
21
35
57
73
65 cFyigc.loa4ddRiteicoyncrleinagctiostnu.dies of the Cu O@{Mo } in the azide–alkyne
2
36
10
11
12
H2O
H2O
H2O
To address the leaching of copper species into solution, the
catalytically active particles were removed from the reaction by
70 ffiillttrraatteionwaatshmalofnthiteorreedacftioornctoimnteiniuneadsaepctairvaittey.exTpheerimreesunlttsansdhtohwe
that the reaction did not proceed significantly upon further
treatment of the residual mixture under similar reaction condition
for second half of the reaction, indicating that no catalytically
75 aTchteiveIRCuspreecmtrauimnedofinththeereficltyrcalteed. catalyst Cu2O@{Mo36} shows
no vibrational changes indicating a good stability of the catalyst
(Fig. 5).
35 aEbnocvoeu,ragtehde bysctohpeeeffoicfienthcye ofretahcetiorenactiwoansproextoacmoilndeedscrwibiethd
Cu2O@{Mo36}under air at 70°C. First, various benzyl chlorides
were investigated and reacted with phenylacetylenes. As shown
in Table 2, benzyl chlorides and phenyl acetylenes with the
40 sounbtshtietuptihoennoylf erilnecgtrwonerwe isthuditraabwleincgyacnlodaedldeictitoronnpdaorntnaetirnsgagnrdoudpids
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1. R. Huisgen, 1,3ꢀDipolar Cycloaddition Chemistry; Padwa, A.,
Ed.; Wiley: New York, 1984.
2. D. S. Pedersen and A. Abell, Eur. J. Org. Chem., 2011,
2399–2411.
3. K. Nwe and M. W. Brechbiel, Cancer Biother.
Radiopharm., 2009, 24, 289–302.
4. K. F. Donnelly, A. Petronilho and M. Albrecht, Chem.
Commun. 2013, 49, 1145–1159.
5. S. G. Agalave, S. R. Maujan and V.S. Pore, Chem. Asian J.
2011, 6, 2696–2718.
6. P. Thirumurugan, D. Matosiuk and K. Jozwiak, Chem. Rev.,
2013, 113, 4905–4979.
7. F. Wang, H. Fu, Y. Jiang and Y. Zhao, Green Chem., 2008,
10, 452–456.
45
50
55
60
65
70
75
80
85
90
95
Fig. 5 IR spectrum of fresh (red line) and reused catalyst Cu2O@{Mo36}
(blue line)
5
A reaction mechanism proposed for the Cu2O@{Mo36} catalysed
1,3ꢀdipolar cycloaddition of terminal alkynes with azides is
outlined in Scheme 2 on the basis of the previous reports [39].
During the reaction, it is proposed that Cu2O are attracted
8.
C. R. Becer, R. Hoogenboom and U.S. Schubert, Angew.
Chem., Int. Ed., 2009, 48, 4900–4908.
10 itnowtahredsftihrsetphsteenpy.laNceetxytl,enteheto afozirdmeaiCntue(rIa)c–tascewtyilthidintheecocmopppleexr
acetylide through coordination interactions and forms a sixꢀ
membered copper metallacycle, which forms a copper triazole
complex on ring contraction. Finally, protonolysis of the copper
15 tthrieazcoaltealcyostm. plex gives the 1,2,3ꢀtriazole product and regenerates
9. F. Himo, T. Lovell, R. Hilgraf, V.V. Rostovtsev, L.
Noodleman, K. B. Sharpless and V. V. Fokin, J. Am. Chem.
Soc., 2005, 127, 210–216.
10. J. E. Moses and A. D. Moorhouse, Chem. Soc. Rev. 2007, 36,
1249–1262.
11. F. Alonso, Y. Moglie, G. Radivoy and M. Yus, Eur. J. Org.
Chem., 2010, 2010, 1875–1884.
12. E. J. Yoo, M. Ahlquist, S. H. Kim, I. Bae, V. V. Fokin, K. B.
Sharpless and S. Chang, Angew. Chem.,Int. Ed., 2007, 46,
1730–1733.
13. D. Wang, N. Li, M. Zhao, W. Shi, C. Ma and B. Chen, Green
Chem., 2010, 12, 2120–2123.
14. Z. Zhang, C. Dong, C. Yang, D. Hu, J. Long, L. Wang, H. Li,
Y. Chen and D. Kong, Adv. Synth. Catal., 2010, 352, 1600–
1604.
15. C. Shao, R. Zhu, S. Luo, Q. Zhang, X. Wang and Y. Hu,
Tetrahedron Lett., 2011, 52, 3782–3785.
16. H. LópezꢀRuiz, J. E. de la CerdaꢀPedro, S. RojasꢀLima, I.
PérezꢀPérez, B. V. RodríguezꢀSánchez, R. Santillán and O.
Coreño, ARKIVOC, 2013, 139–164.
17. M. N. S. Rad, S. Behrouz, A. Movahedian, M. M.
Doroodmand, Y. Ghasemi, S. RasoulꢀAmini, A.ꢀR. A.
Gandomani and R. Rezaie, Helv. Chim. Acta, 2013, 96, 688–
701.
18. K. Wang, X. Bi, S. Xing, P. Liao, Z. Fang, X. Meng, Q.
Zhang, Q. Liu and Y. Ji, Green Chem., 2011, 13, 562–565.
19. I. Prakash, P. Muralidharan, N. Nallamuthu, M.
Venkateswarlu and N. Satyanarayana, Mater. Res. Bull. 2007,
42, 1619–1624.
20. A. Mateen, J. Pak. Mater. Soc. 2008, 2, 40ꢀ43.
21. L. Gou and C.J. Murphy, Nano Lett. 2003, 3, 231–234.
22. R. G. Finke and S. Oezkar, Coord. Chem. Rev., 2004, 248,
135–146.
23. S. Oezkar and R. G. Finke, J. Am. Chem. Soc., 2002, 124,
5796–5810.
Scheme 2 Proposed mechanism of Cu2O@{Mo36}catalytic cycle for the
formation of 1,2,3ꢀtriazole.
20 Conclusions
In
conclusion
the
polar
surface
of
a
polyoxomolybdate(NH4)12[Mo36(NO)4O108(H2O)16] was used as a
support and stabilization scaffold for Cu2O nanoparticles of 10–
25 b3e0ennmsusiczcee.sTsfhuilslyisdtheemfoinrssttrtaimteedthasatasuhcihghalycoemffpiociseitnet sryesctyecmlahbales
catalyst for the synthesis of 1,2,3ꢀtriazoles by the azide–alkyne
cycloaddition.
24. R. G. Finke, Metal Nanoparticles, 2002, 17–54.
25. A. Troupis, A. Hiskia and E. Papaconstantinou, Angew.
Chem. Int. Ed., 2002, 41, 1911–1914.
26. V. Kogan, Z. Aizenshtat, R. PopovitzꢀBiro and R. Neumann,
Org. Lett., 2002, 4, 3529–3532.
30 MAc.kAnomwinleidgthmaneknststhe Research Council of the University of
27. X. L´opez, J. A. Fern´andez and J. M. Poblet, Dalton Trans.,
2006, 1162–1167.
28. J. J. Borr´asꢀAlmenar, E. Coronado, A. Mửller and M. T.
Pope, Polyoxometalate Molecular Science, Kluwer Academic
Publishers, Dordrecht, 2003.
100
Maragheh for financial support of this work.
29. M. T. Pope, Heteropoly and IsopolyOxometalates, Springerꢀ
Verlag. Berlin, 1983.
105
30. M. Sadakane and E. Steckhan, Chem. Rev., 1998, 98, 219–
237.
31. R. Contant and G. Hervé, Rev. Inorg. Chem. 2002, 22, 63–
111.
32. DꢀL. Long, R. Tsunashima and L. Cronin, Angew. Chem.,
Int. Ed. 2010, 49, 1736– 1758.
33. J. Song, Z. Luo, D. K. Britt, H. Furukawa, O. M. Yaghi, K. I.
Hardcastle and C. L. Hill, J. Am. Chem. Soc. 2011, 133,
16839– 16846.
Notes and references
aDepartment of Chemistry, Faculty of Science, University of Maragheh,
35 P.O. Box. 55181-83111731, Maragheh, Iran; mamini@maragheh.ac.ir
bDepartment of Chemistry, University of Tehran, Tehran, Iran
c
110
Advanced Analysis Center, Korea Institute of Science and Technology,
Seoul 136-791, South Korea; khchae@kist.re.kr (K.H.Chae)
dDr. SS Bhatnagar, University Institute of Chemical Engineering &
40 Technology(SSB UICET), Panjab University Chandigarh, 160-014, India
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 4

Page 5 of 6
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View Article Online
DOI: 10.1039/C6NJ00868B
34. C.ꢀY. Sun, SꢀX. Liu, DꢀD. Liang, KꢀZ. Shao, YꢀH. Ren and Zꢀ
M. Su, J. Am. Chem. Soc. 2009, 131, 1883– 1888
35. HꢀY. Liu, GꢀH. Wang, J. Yang, YꢀY. Liu and JꢀF. Ma, Inorg.
Chem. Commun. 2014, 50, 92ꢀ96.
5
36. M. Amini, H. Naslhajian, S.M.F. Farnia and M. Hołyńska,
Eur. J. Inorg. Chem. 2015, 2015, 3873–3878.
37. X. Qiu, M. Liu, K. Sunada, M. Miyauchi and K. Hashimoto,
Chem. Commun. 2012, 48, 7365−7367.
38. X. Qiu, M. Miyauchi, K. Sunada, M. Minoshima, M. Liu, Y.
Lu, D. Li, Y. Shimodaira, Y. Hosogi and Y. Kuroda, ACS
Nano 2012, 6, 1609−1618.
10
39. P. Veerakumar, M. Velayudham, KꢀL. Lu, S. Rajagopal,
Catal. Sci. Technol., 2011, 1, 1512–1525.
15
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Graphical Abstract
A Cu2O@ ({Mo36} composite has been utilized as a recyclable catalyst for the Huisgen 1,3-dipolar
cycloaddition reaction.