Green Chemistry
DOI: 10.1039/C3GC41154K
°
Chem. Int. Ed. 2012, 51, 5062. (c) H. Li, C. C. C. J. Seechurn, T. J.
Colacot, ACS Catal. 2012, 2, 1147.
ppm 1 catalyst in oꢀxylene at 130 C. Table 3 shows that 1 is
highly active in oꢀxylene for this reaction, in addition, 1 can
be recycled and reused three times without obvious losing its
catalytic activity, especially the catalyst loading at 2500
ppm. To determine if the heterogeneous or the dissolved
homogeneous Pdꢀspecies were the real catalysts responsible
2
For various types of homoꢀ and heterogeneous Pdꢀcatalysts for Suzukiꢀ
Miyaura reaction, see: (a) O. Navarro, III, R. A. Kelly, S. P. Nolan, J.
Am. Chem. Soc. 2003, 125, 16194. (b) Y. M. A. Yamada, S. M.
Sarker, Y. Uozumi, J. Am. Chem. Soc. 2012, 134, 3190. (c) S.ꢀY.
Ding, J. Gao, Q. Wang, Y. Zhang, W.ꢀG. Song, W. Wang, J. Am.
Chem. Soc. 2011, 133, 19816. (d) F. Wang, C. Li, L.ꢀD. Sun, C.ꢀH.
Xu, J. Wang, J. C. Yu, C.ꢀH. Yan, Angew. Chem. Int. Ed. 2012, 51,
4872. (e) V. A. Zinovyeva, M. A. Vorotyntsev, I. Bezverkhyy, D.
Chaumont, J.ꢀC. Hierso, Adv. Funct. Mater. 2011, 21, 1064. (f) B. Li,
Z. Guan, W. Wang, X. Yang, J. Hu, B. Tan, T. Li, Adv. Mater. 2012,
6
7
7
8
8
9
5
0
5
0
5
0
1
3
5
0
5
0
5
0
for the coupling reaction between PhBr and PhB(OH) , the
2
following control experiment was carried out. The solid
catalyst was filtered after the reaction completion (based on
HPLC). Then the starting materials are added to this filtrate,
and the reaction system was allowed to stir at 130 C in air, no
yield and conversion changes based on HPLC were detected.
Moreover, the XPS analysis was performed on the filtrate, and
no Pdꢀspecies was found, indicating the reaction is
heterogeneous catalytic process. (Supporting Information).
In summary, we report in this contribution the facile and
efficient synthesis of Pd L nanoball decorated with fiveꢀ
membered oxadiazole moiety based on a new molecular
tripod. The strategy developed herein provides an alternative
approach to access functionalized metallosupramolecules
which are not accessible via conventional coordinationꢀdriven
selfꢀassembly based on simple bidentate linkers. The nanoꢀ
sized Pd L ball was demonstrated as an excellent catalyst for
2
4, 3390.
1
1
2
2
3
3
4
Recent reviews: (a) R. Chakrabarty, P. S. Mukherjee, P. J. Stang,
Chem. Rev. 2011, 111, 6810. (b) M. J. Maarten, I. A. Smulders, C. B.
Riddell, R. N. Jonathan, Chem. Soc. Rev. 2013, Advance Article DOI:
°
1
0.1039/C2CS35254K. (c) N. B. Debata, D. Tripathy, D. K. Chand,
Coord. Chem. Revs. 2012, 256, 1831.
Typical molecular Pd L cages since 1995: (a) M. Fujita, D. Oguro,
a
6
8
M. Miyazawa. H. Oka, K. Yamaguchi, K. Ogura, Nature 1995, 378,
69. (b) M. Hong, Y. Zhao, W. Su, R. Cao, M. Fujita, Z. Zhou, A. S.
4
C. Chan, J. Am. Chem. Soc. 2000, 122, 4819. (c) D. K. Chand, K.
Biradha, M. Fujita, S. Sakamoto, K. Yamaguchi, Chem. Commun.
6
8
2
002, 2486. (d) D. Moon, S. Kang, J. Park, K. Lee, R. P. John, H.
Won, G. H. Seong, Y. S. Kim, G. H. Kim, H. Rhee, M. S. Lah, J. Am.
Chem. Soc. 2006, 128, 3530. (e) S. Hiraoka, Y. Yamauchi, R.
Arakane, M. Shionoya, J. Am. Chem. Soc. 2009, 131, 11646. (f) T. K.
Ronson, C. Carruthers, J. Fisher, T. Brotin, L. P. Harding, P. J.
Rizallah, M. J. Hardie, Inorg. Chem. 2010, 49, 675. (g) H. K. Liu, X.
Tong, Chem. Commun. 2002, 1316. (h) S. Ghosh, P. S. Mukherjee, J.
Org. Chem. 2006, 71, 8412. (i) T. K. Ronson, J. Fisher, L. P. Harding,
M. J. Hardie, Angew. Chem. Int. Ed. 2007, 46, 9086. j) S. Hiraoka, K.
Harano, M. Shiro, Y. Ozawa, N. Yasuda, K. Toriumi, M. Shionoya,
Angew. Chem. Int. Ed. 2006, 45, 6488. (k) M. Yoneya, T. Yamaguchi,
S. Sato, M. Fujita, J. Am. Chem. Soc. 2012, 134, 14401.
6
8
typical SuzukiꢀMiyaura crossꢀcoupling reactions. It is worthy
of note that the Pd L ꢀball can be both the homoꢀ and
6
8
heterogeneous catalysts in different solvent systems, and can
catalyze CꢀC crossꢀcoupling reactions under ambient
conditions in very high yields. The other kinds of organic
coupling reactions catalyzed by 1 are currently investigated in
our lab.
95
00
05
10
15
20
5
(a) S. Sato, J. Lida, K. Suzuki, M. Kawano, T. Ozeki, M. Fujita,
Science 2006, 313, 1273. (b) P. Mal, B. Breiner, K. Rissanen, J. R.
Nitschke, Science 2009, 324, 1697. (c) R. Custelcean, P. V. Bonnesen,
N. C. Duncan, X. Zhang, L. A. Watson, G. V. Berkel, W. B. Parson,
B. P. Hay, J. Am. Chem. Soc. 2012, 134, 8525. (d) M. Yoshizawa, M.
Tamura, M. Fujita, Science 2006, 312, 251. (e) M. D. Pluth, R. G.
Bergman, K. N. Raymond, Science 2007, 316, 85. (f) P. Mal, B.
Breiner, K. Rissanen, J. R. Nitschke, Science 2009, 324, 1697. (g) O.
Chepelin, J. Ujma, X. Wu, A. M. Z. Slawin, M. B. Pitak, S. J. Coles,
J. Michel, A. Jones, P. E. Barran, P. J. Lusby, J. Am. Chem. Soc.
2012, 134, 19334.
1
1
1
1
1
Acknowledgments
We are grateful for financial support from 973 Program
Grant Nos. 2013CB933800 and 2012CB821705), NSFC
Grant Nos. 91027003, 21072118 and 21271120) and
(
(
6
To our knowledge, only one preliminary study related to coordinationꢀ
driven Pd(II)ꢀcage (Pd
Miyaura reactions was reported. The reactions were carried out under
relative vigorous conditions (0.01 mol % of Pd , anhydrous DMF,
00 C), generating the corresponding coupling products in moderate
3 2
L ) as homogeneous catalyst for Suzukiꢀ
35
“PCSIRT”.
3 2
L
°
2
Notes and references
a
yields. Please see: T. H. Noh, E. Heo, K. H. Park, O.ꢀS. Jung, J. Am.
Chem. Soc. 2011, 133, 1236.
(a) Y.ꢀB. Dong, P. Wang, J.ꢀP. Ma, X.ꢀX. Zhao, H.ꢀY. Wang, B. Tang,
R.ꢀQ. Huang, J. Am. Chem. Soc. 2007, 129, 4872. (b) P. Wang, J.ꢀP.
Ma, Y.ꢀB. Dong, R.ꢀQ. Huang, J. Am. Chem. Soc. 2007, 129, 10620.
(c) Q.ꢀK. Liu, J.ꢀP. Ma, Y.ꢀB. Dong, J. Am. Chem. Soc. 2010, 132,
7005.
College of Chemistry, Chemical Engineering and Materials Science,
7
8
Key Laboratory of Molecular and Nano Probes, Engineering Research
Center of Pesticide and Medicine Intermediate Clean Production,
Ministry of Education, Shandong Provincial Key Laboratory of Clean
Production of Fine Chemicals, Shandong Normal University, Wenhua
East Road, Jinan 250014, People’s Republic of China. E-mail:
Electronic Supplementary Information (ESI) available: Experimental
procedures, including synthesis, characterization, crystal data and
detailed in catalytic reactions. See DOI: 10.1039/b000000x/
L (NO )12 (1): A mixture of L
6 8 3
79.6 mg, 10 mmol) and palladium nitrate (23.0 mg, 10 mmol) was
dissolved in DMSO (4 mL). This mixture was heated to 70°C for 2 h.
After cooled to room temperature, dichloromethane (4 mL) and diethyl
ether (20 mL) were added to the reaction system. The resulting precipitate
40
45
50
Q.ꢀF. Sun, J. Iwasa, D. Ogawa, Y. Ishido, S. Sato, T. Ozeki, Y. Sei, K.
Yamaguchi, M. Fujita, Science 2010, 328, 1144.
9
1
1
L. Allouche, A. Marquis, J.ꢀM. Lehn, Chem. Eur. J. 2006, 12, 7520.
0 E. S. Sidharth, T. Pradeep, Chem. Mater. 2011, 23, 989.
1 The measured XRPD pattern (Supporting Information, Fig. S2) of 1 is
†
12+
almost
identical
to
that
oi f
[Pd
6
L
8
]
(L
=
‡
Synthesis and Characterization of Pd
4
1
1
1
25
30
35
tris(isonocotinoyl)cyclotriguaiacylene).
(
1
2
Now some SuzukiꢀMiyaura reactions which are catalyzed by Pdꢀ
loaded nano hybrid materials in water to air without any palladiumꢀ
phosphine complex involvement are reported. (a) Z. Zhang, Z, Wang,
J. Org. Chem. 2006, 71, 7485. (b) J. M. Chalker, C. S. C. Wood , B.
G. Davis, J. Am. Chem. Soc., 2009, 131, 16346. (c) R. Narayanan, M.
A. ElꢀSayed, J. Am. Chem. Soc., 2003, 125, 8340.
1
was collected by centrifugation as white powder. Yield 98 %. H NMR
(
300 MHz, DMSO, 25°C, TMS): 9.65 (d, J = 5.1 Hz, 48H, C
d, J = 5.6 Hz, 48H, C NH ), 2.13 (48H, C ), 0.81 (t, J = 7.2 Hz, 72H,
). IR (KBr pellet) [(cm )]: 2979(m), 1624(m), 1541(m), 1482(m),
384(s), 1219(w), 1101(w), 1058(m), 966(w), 836(m), 709(w), 531(w).
Anal. Calcd for Pd 84: Pd, 10.36; C, 51.44; H, 3.53; N, 19.09.
Found: Pd, 10.39; C, 51.45; H, 3.50; N, 19.11.
5 4
NH ), 8.36
(
5
4
2 5
H
ꢀ1
13 To the best of our knowledge, 1 is the first highly active homoꢀ and
heterogeneous catalyst based on coordinationꢀdriven supramolecular
complexes for crossꢀcoupling reactions. Although the catalytic
mechnism of 1 is not clear, it is believed to be the same as those of
many other molecular Pd(II)ꢀcomplexes (Supporting Information).
5
5
0
2 5
C H
1
6 264 216 60
C H O N
1
(a) N. Miyaura, T. Yanagi, A. Suzuki, Synthesis, 1981, 513. (b) C. C.
C. J. Seechurn, M. O. Kitching, T. J. Colacot, V. Snieckus, Angew.
6
4
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