´
5 L. D. PachOn and G. Rothenberg, Appl. Organomet. Chem., 2008,
22, 288.
6 Y. L. Gua and G. X. Li, Adv. Synth. Catal., 2009, 351, 817.
7 E. Redel, J. Kra¨mer, R. Thomann and C. Janiak, J. Organomet.
Chem., 2009, 694, 1069.
8 P. Migowski, G. Machado, S. R. Texeira, Maria. C. M. Alves, J.
Morais, A. Traverse and J. Dupont, Phys. Chem. Chem. Phys., 2007,
9, 4814.
9 G. S. Fonseca, A. P. Umpierre, P. F. P. Fichtner, S. R. Teixeira and
J. Dupont, Chem. Eur. J., 2003, 9, 3263.
10 E. T. Silveira, A. P. Umpierre, L. M. Rossi, G. Machado, J. Morais,
G. V. Soares, I. J. R. Baumvol, S. R. Teixeira, P. F. P. Fichtner and
J. Dupont, Chem.–Eur. J., 2004, 10, 3734.
11 L. M. Rossi, J. Dupont, G. Machado, P. F. P. Fichtner, C. Radtke,
I. J. R. Baumvol and S. R. Teixeira, J. Braz. Chem. Soc., 2004, 15,
904.
12 G. S. Fonseca, E. T. Silveira, M. A. Gelesky and J. Dupont, Adv.
Synth. Catal., 2005, 347, 847.
13 N. Yan, C. Zhao, C. Luo, P. J. Dyson, H. C. Liu and Y. Kou, J. Am.
Chem. Soc., 2006, 128, 8714.
14 S. D. Miao, Z. M. Liu, B. X. Han, J. Huang, Z. Y. Sun, J. L. Zhang
and T. Jiang, Angew. Chem., Int. Ed., 2006, 45, 266.
15 J. Wang, J. Feng, R. Qin, H. Fu, M. Yuan, H. Chen and X. Li,
Tetrahedron: Asymmetry, 2007, 18, 1643.
Fig. 5 IR spectra of H2S absorbed on PtNPs (raw data, black
line), fitting of symmetric vibrations of H2S (blue line), fitting for
antisymmetric vibrations of H2S (green line) after the adsorption of
H2S on (A) PtNP–[Bmim][BF4] and (B) Pt–[C2Omim][BF4] (difference
spectra: after H2S adsorption minus spectrum without H2S – pink line).
The red line corresponds to the sum of the blue and green lines.
16 M. H. G. Prechtl, M. Scariot, J. D. Scholten, G. Machado, S. R.
Teixeira and J. Dupont, Inorg. Chem., 2008, 47, 8995.
17 G. S. Fonseca, A. P. Umpierre, P. F. P. Fichtner, S. R. Teixeira and
J. Dupont, Chem. Eur. J, 2003, 9, 3263.
18 X. D. Mu, D. G. Evans and Y. A. Kou, Catal. Lett., 2004, 97,
suggesting the OH groups in [C2OHmim][BF4] help to weaken
the interaction of H2S on the surface of the PtNPs. The H2S-IR
test gave further evidence for the presence of weak interactions
between the PtNPs and OH groups in the IL. Moreover, the
experiment indicates that the PtNPs in the hydroxyl group
functionalized IL is poison resistant as it weakens the adsorption
of poison (H2S) molecule to the metal surface.
151.
19 X. D. Mu, J. Q. Meng, Z. C. Li and Y. Kou, J. Am. Chem. Soc., 2005,
127, 9694.
20 C. Zhao, H. Z. Wang, N. Yan, C. X. Xiao, X. D. Mu, P. J. Dyson and
Y. Kou, J. Catal., 2007, 250, 33.
21 I. S. Park, M. S. Kwon, K. Y. Kang, J. S. Lee and J. Parka, Adv. Synth.
Catal., 2007, 349, 2039.
22 M. J. Jacinto, P. K. Kiyohara, S. H. Masunaga, R. F. Jardim and
L. M. Rossi, Appl. Catal.,A, 2008, 38, 52.
23 X. Yang, N. Yan, Z. Fei, R. M. C. Quesada, G. Laurenczy, L. K.
Minsker, Y. Kou, Y. Li and P. J. Dyson, Inorg. Chem., 2008, 47, 7444.
24 J. Dupont, G. S. Fonseca, A. P. Umpierre, P. F. P. Fichtner and S. R.
Teixeira, J. Am. Chem. Soc., 2002, 124, 4228.
25 G. S. Fonseca, J. D. Scholten and J. Dupont, Synlett., 2004, 1525.
26 G. S. Fonseca, G. Machado, S. R. Teixeira, G. H. Fecher, J. Morais,
M. C. M. Alves and J. Dupont, J. Colloid. Interface. Sci., 2006, 301,
193.
Conclusions
A highly effective PtNP–IL system has been established for
the selective synthesis of aromatic chloroamines from aromatic
chloronitro compounds. Compared to other catalytic systems
employing NPs or heterogeneous catalysts operating in molec-
ular organic solvents, the PtNP–IL systems described herein
exhibit excellent selectivity to the desired product, and the
hydroxyl-functionalized IL system, display excellent stability
allowing extensive recycling and high turnover numbers. This
system provides a further example of an IL–catalyst regime
which offers environmental benefits in terms of eliminating
organic solvents from the catalytic process, although on this
laboratory scale, organic solvents were used to extract the
product. Moreover, and importantly, based on experimental
evidence the role of the ILs can be directly ascribed to the high
selectivity obtained and the high catalyst stability.
27 G. S. Fonseca, J. B. Domingos, F. Nome and J. Dupont, J. Mol.
Catal., A, 2006, 248, 10.
28 J. D. Scholten, G. Ebeling and J. Dupont, Dalton Trans., 2007, 5554.
29 L. S. Ott, S. Campbell, K. R. Seddon and R. G. Finke, Inorg. Chem.,
2007, 46, 10335.
30 Y. Zhu, C. Koh, A. T. Peng, A. Emi, W. Monalisa, L. K. J. Louis,
N. S. Hosmane and J. A. Maguire, Inorg. Chem., 2008, 47, 5756.
31 J. Huang, T. Jiang, B. Han, H. Gao, Y. Chang, G. Zhao and W. Wu,
Chem. Commun., 2003, 1654.
32 J. Huang, T. Jiang, H. Gao, B. Han, Z. Liu, W. Wu, Y. Chang and
G. Zhao, Angew. Chem. Int. Ed., 2004, 43, 1397.
33 J. Le Bras, D. K. Mukherjee, S. Gonzalez, M. Tristany, B.
Ganchegui, M. Moreno-Manas, R. Pleixats, F. Henin and J. Muzart,
New J. Chem., 2004, 28, 1550.
34 A. P. Umpierre, G. Machado, G. H. Fecher, J. Morais and J. Dupont,
Adv. Synth. Catal., 2005, 347, 1404.
35 C. W. Scheeren, G. Machado, J. Dupont, P. F. P. Fichtner and S. R.
Texeira, Inorg. Chem., 2003, 42, 4738.
36 C. W. Scheeren, G. Machado, S. R. Teixeira, J. Morais, J. B. Domingos
and J. Dupont, J. Phys. Chem. B, 2006, 110, 13011.
37 C. X. Xiao, H. Z. Wang, X. D. Mu and Y. Kou, J. Catal., 2007, 250,
25.
Acknowledgements
This work was supported by the National Science Foundation
of China (Project Nos 20773005, 20533010).
38 T. J. Geldbach, D. B. Zhao, N. C. Castillo, G. Laurenczy, B.
Weyershausen and P. J. Dyson, J. Am. Chem. Soc., 2006, 128, 9773.
39 D. B. Zhao, Z. F. Fei, T. J. Geldbach, R. Scopelliti and P. J. Dyson,
J. Am. Chem. Soc., 2004, 126, 15876.
40 F. Fei, D. B. Zhao, D. Pieraccini, W. H. Ang, T. J. Geldbach, R.
Scopelliti, C. Chiappe and P. J. Dyson, Organometallics, 2007, 26,
1588.
References
1 P. J. Dyson, Appl. Organomet. Chem., 2002, 16, 495.
2 D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem., Int. Ed., 2005,
44, 7852.
3 P. Migowski and J. Dupont, Chem.–Eur. J., 2007, 13, 32.
4 V. I. Parvulescu and C. Hardacre, Chem. Rev., 2007, 107, 2615.
232 | Green Chem., 2010, 12, 228–233
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