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ChemComm
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Journal Name
literature and our Au/BC-1 catalyst at different temperatures. (Au mol %: I
0.00076, II 0.000077, III 0.000038, IV 0.000026.)
Foundation of China (21722103, 21931005, 21720102002, and
DOI: 10.1039/D0CC06764D
21673140), Shanghai Science and Technology Committee
Cleavage of the C-Br bonds of preadsorbed (1-bromoethyl) (19JC1412600) and the SJTU-MPI partner group.
benzene on Au/BC-1 is exothermic by 0.47 eV (Figure 4a). Unlike
the unchanged configuration of (1-bromoethyl) benzene on
Au/C, the calculated configurations of (1-bromoethyl) benzene
Conflicts of interest
on the electron-deficient Au of Au/BC-1 exhibit an automatic
cleavage of C-Br bonds, resulting in the formation of a benzylic
radical and a Br atom adsorbed on the Au surface (Figures 4d
and S13, and Supplementary Videos 1-2), indicating a radical
pathway for the coupling process, as experimentally validated
by the observed homocoupling process (Figure S14). The
predicted catalytic mechanism was demonstrated in Figure S15.
After determining the dominant effect of electron density on
the activity of Au nanoparticles, we were able to experimentally
tune the intrinsic activity of Au nanoparticles, as indicated by
the TOF values, by changing the type and concentration of
dopants (Figure 4e and Table S6). The TOF values for coupling
(1-bromoethyl) benzene with allyltributylstannane over Au
nanoparticles under fixed reaction conditions could be greatly
increased from 4549 h-1 to 10026 h-1 and then to 14729 h-1 for
the Au/C, Au/BC-0.5 and Au/BC-1 samples, respectively, with
increasing electron deficiency, indicating the adjustable activity
of Au nanoparticles along with the increased concentrations of
There are no conflicts to declare.
Notes and references
1
2
N. Huang, Y. Xu and D. Jiang, Sci. Rep., 2014, 4, 7228.
M. J. Jin and D. H. Lee, Angew. Chem. Int. Ed., 2010, 49,
1119.
3
4
C. Cordovilla, C. Bartolomé, J. M. Martínez-Ilarduya and P.
Espinet, ACS Catal., 2015, 5, 3040.
A. Ghorbani-Choghamarani and M. Norouzi, New J. Chem.,
2016, 40, 6299.
5
6
M. Stratakis and H. Garcia, Chem. Rev., 2012, 112, 4469.
T.-N. Ye, Y. Lu, Z. Xiao, J. Li, T. Nakao, H. Abe, Y. Niwa, M.
Kitano, T. Tada and H. Hosono, Nat. Commun., 2019, 10,
5653.
7
8
9
M. Pagliaro, V. Pandarus, R. Ciriminna, F. Beland and P. D.
Cara, ChemCatChem, 2012, 4, 432.
J. Holz, C. Pfeffer, H. Zuo, D. Beierlein, G. Richter, E. Klemm
and R. Peters, Angew. Chem. Int. Ed., 2019, 58, 10330.
Y.-X. Lin, S.-N. Zhang, Z.-H. Xue, J.-J. Zhang, H. Su, T.-J. Zhao,
G.-Y. Zhai, X.-H. Li, M. Antonietti and J.-S. Chen, Nat.
Commun., 2019, 10, 4380.
boron dopants. As
a control sample, electron-rich Au
nanoparticles (Figure S16) embedded in nitrogen-doped
carbons provide a TOF value of only 1040 h-1 and perform even
worse than Au/C, again demonstrating the unique role of
electron-deficient Au in activating C-Br bonds for the Stille
coupling reaction.
10 Y.-X. Liu, H.-H. Wang, T.-J. Zhao, B. Zhang, H. Su, Z.-H. Xue, X.-
H. Li and J.-S. Chen, J. Am. Chem. Soc., 2019, 141, 38.
11 Z.-H. Xue, J.-T. Han, W.-J. Feng, Q.-Y. Yu, X.-H. Li and J.-S.
Chen, Angew. Chem. Int. Ed., 2018, 57, 2697.
12 H. Su, P. Gao, M.-Y. Wang, G.-Y. Zhai, J.-J. Zhang, T.-J. Zhao, J.
Su, M. Antonietti, X.-H. Li and J.-S. Chen, Angew. Chem. Int.
Ed., 2018, 57, 15194.
With optimized Au/substrate ratios, the best Au/BC-1 catalyst
with the most pronounced electron deficiency exhibited a TOF
of 17329 h-1 at 50 °C and a remarkably high TOF of 5199 h-1 at
room temperature (Figures 4f and S17 and Table S7). The TOF
value of Au/BC-1 at 50 °C is four times that of the reported
Au/AC catalyst. To the best of our knowledge, there is a rather
limited number of effective catalysts that could trigger similar
reactions at room temperature reported in the literature and
confirmed experimentally in this work (Entry 8 in Table S7). The
state-of-the-art homogeneous catalyst Pd(AsPh3)2 exhibited a
TOF value of only 30 h-1 at room temperature,26 demonstrating
the great potential of heterojunction-based nanocatalysts as
highly efficient catalysts for real-life chemical production.
In conclusion, we designed an electron-deficient Au
nanoparticle-based catalyst via Schottky contact with boron-
doped carbons for room-temperature Stille cross-coupling
reactions. The electron deficiency of the Au nanoparticles
significantly increased the automatic activation of C-Br bonds in
alkylbromides and successive coupling reactions with
allylstannanes, surpassing the activity of reported
homogeneous catalysts. Tuning the electron density of the Au
nanoparticles provided new insights into the design of highly
efficient and reusable catalysts for organic synthesis under mild
conditions, enhancing the potential of heterogeneous noble
metal catalysts to make the manufacture of fine chemicals
environmentally friendly.
13 L. Yin and J. Liebscher, Chem. Rev., 2007, 107, 133.
14 X. Zhang, Z. Sun and B. Wang, J. Am. Chem. Soc., 2018, 140,
954.
15 Q. Gu, Q. Jia, J. Long and Z. Gao, ChemCatChem, 2019, 11,
669.
16 G. Lu, C. Cai and B. H. Lipshutz, Green Chem., 2013, 15, 105.
17 J. C. Garcia-Martinez, R. Lezutekong and R. M. Crooks, J. Am.
Chem. Soc., 2005, 127, 5097.
18 L. He, F. Weniger, H. Neumann and M. Beller, Angew. Chem.
Int. Ed., 2016, 55, 12582.
19 X.-H. Li, M. Baar, S. Blechert and M. Antonietti, Sci. Rep.,
2013, 3, 1743.
20 Z.-H. Xue, S.-N. Zhang, Y.-X. Lin, H. Su, G.-Y. Zhai, J.-T. Han,
Q.-Y. Yu, X.-H. Li, M. Antonietti and J.-S. Chen, J. Am. Chem.
Soc., 2019, 141, 14976.
21 X.-H. Li and M. Antonietti, Chem. Soc. Rev., 2013, 42, 6593.
22 Y. Jia, R. Hu, Q. Zhou, H. Wang, X. Gao and J. Zhang, J. Catal.,
2017, 348, 223.
23 Y. Cai, Y. Guo and J. Liu, Chem. Commun., 2020, 56, 876.
24 Z. Chen, E. Vorobyeva, S. Mitchell, E. Fako, M. A. Ortuno, N.
Lopez, S. M. Collins, P. A. Midgley, S. Richard, G. Vile and J.
Perez-Ramirez, Nat. Nanotechnol., 2018, 13, 702.
25 T.-N. Ye, S.-W. Park, Y. Lu, J. Li, M. Sasase, M. Kitano, T. Tada
and H. Hosono, Nature, 2020, 583, 391.
26 T. O. Ronson, J. R. Carney, A. C. Whitwood, R. J. K. Taylor and
J. S. Fairlamb, Chem. Commun., 2015, 51, 3466.
4 | J. Name., 2012, 00, 1-3
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