C, 44.03; H, 4.55, N, 7.90, ESI-MS: m/z 318.92, (M-Cl+,
98%).
Catalysis, Angew. Chem., Int. Ed. Engl., 1994, 33, 2144; (h) H. Bricout,
F. Hapiot, A. Ponchel, S. Tilloy and E. Monflier, Sustainability, 2009,
1, 924; (i) B. Cornils, Org. Process Res. Dev., 1998, 2, 121.
2 (a) B. Cornils and E. Wiebus, Chemtech., 1995, 25, 33; (b) B. Cornils
and E. G. Kuntz, J. Organomet. Chem., 1995, 502, 177.
3.7 General hydroformylation procedure
3 (a) A. Riisager, K. M. Erikson, J. Hjortkjaer and R. Fehrmann,
J. Mol. Catal. A: Chem., 2003, 193, 259–272; (b) M. E. Davis, in
Aqueous-Phase Organometallic Catalysis, ed., B Cornils and W. A.
Hermann, Chapter 4, 7 Wiley, Weinheim, 1998, pp. 241; (c) M. E.
Davis, Chemtech., 1992, 22, 498.
4 (a) Z. K. Lopez-Castillo, R. Flores, I. Kani, J. P. Fackler Jr. and A.
Akgerman, Ind. Eng. Chem. Res., 2008, 42, 3893; (b) C. Halm, M. J.
Kurth and Angew, Angew. Chem., Int. Ed., 1998, 37, 510.
5 (a) J. S. Wilkes, Green Chem., 2002, 4, 73; (b) J. L. Anthony, E. J.
Maginn and J. F. Brennecke, J. Phys. Chem. B, 2002, 106, 7315; (c) J.
S. Wilkes, J. Mol. Catal. A: Chem., 2004, 214, 11.
6 (a) A. Riisager, K. M. Eriksen, P. Wasserscheid and R. Fehrmann,
Catal. Lett., 2003, 98, 149; (b) A. Riisager, R. Fehrmann, S. Flicker,
R. Van Hal, M. Haumann and P. Wasserscheid, Angew. Chem., Int.
Ed., 2004, 43, 2; (c) Y. Yang, C. Deng and Y. Yuan, J. Catal., 2005,
232, 108.
7 (a) P. Arya, N. Verugopal Rao and J. Singkhonrat, J. Org. Chem.,
2000, 65, 1881; (b) R. Van Heerbeek, P. C. J. Kamer, P. W. N. M. van
Leeuwen and J. N. H Reek, Chem. Rev., 2002, 102, 3717; (c) P. Li and
S. Kawi, J. Catal., 2008, 257, 23.
8 (a) G. O. Evans, C. U. Pittman, R. Mc Millan, R. T. Beach and
R. Jones, J. Organomet. Chem., 1975, 87, 189; (b) F. Shibahara, K.
Nozaki, T. Matsuo and T. Hiyama, Bioorg. Med. Chem. Lett., 2002,
12, 1825; (c) F. Shabahara, K. Nozaki and T. Hiyama, J. Am. Chem.
Soc., 2003, 125, 8555; (d) D. E. Bryant and M. Kilner, J. Mol. Catal.
A: Chem., 2003, 193, 83; (e) E. V. Slivinskii and N. V. Kolesnichenko,
Russ. Chem. Bull., 2004, 53, 2449.
9 (a) M. A. Valenzuela, G. Aguilar, P. Bosch, H. Armendariz, P. Salas
and A. Montoya, Catal. Lett., 1992, 15, 179; (b) A. M. Trzeciak, J.
J. Ziołkowski, Z. Jaworska-Galas, W. Mista and J. Wrzyszcz, J. Mol.
Catal., 1994, 88, 13; (c) J. Wrzyszcz, M. Zawadzki, A. M. Trzeciak
and J. J. Ziołkowski, J. Mol. Catal. A: Chem., 2002, 189, 203; (d) L.
Huang and S. Kawi, Catal. Lett., 2004, 92, 57.
10 (a) J. P. K. Reynhardt, Y. Yang, A. Sayari and H. Alper, Chem.
Mater., 2004, 16, 4095; (b) X. Lan, W. Zhang, L. Yan, Y. Ding, X.
Han, L. Lin and X. Bao, J. Phys. Chem. C, 2009, 113, 6589.
11 (a) E. Guibal, Prog. Polym. Sci., 2005, 30, 71; (b) B. F. Peirano,
V. Thierry, F. Quignard, M. Rabitzer and E. Guibal, J. Membr. Sci.,
2009, 329, 30; (c) D. J. Macquarrie and J. J. E. Hardy, Ind. Eng. Chem.
Res., 2005, 44, 8499; (d) E. Guibal, V. Thierry and B. F. Peirano, Ion
Exch. Solvent Extr., 2007, 18, 151; (e) S.-S. Yi, D.-H. Lee, E. Sin and
Y.-S. Lee, Tetrahedron Lett., 2007, 48, 6771; (f) S. E. S. Leonhardt,
A. Stolle, B. Ondruschka, G. Cravotto, C. De Leo, K. D. Jandt and
T. F. Keller, Appl. Catal., A, 2010, 379, 30.
Hydroformylation reactions were conducted in a 90 ml stainless
steel autoclave. The autoclave was charged with xylene (10 ml),
1-octene (715 mg, 6.37 mmol), n-decane internal standard (180
mg, 1.26 mmol) and one of the Rh catalysts (3, 4, 5 or 6) (2.87
¥ 10-3 mmol, substrate: Rh ratio = 2276 : 1). The autoclave was
flushed three times with syngas (CO : H2, 1 : 1 ratio) followed
by pressurizing and heating to the desired syngas pressure and
temperature respectively. Samples were taken every 2 h and
analysed using gas chromatography (GC). The products were
confirmed in relation to authentic iso-octenes and aldehydes.
4. Conclusions
Two new supported-Rh(I) catalysts based on a sustainable,
biodegradable and non-toxic biopolymer support have been
successfully prepared in a stable form. They were characterized
using several techniques including elemental analysis, UV-vis,
FT-IR, ICP-MS, 31P and 13C solid state NMR spectroscopy,
TEM and PXRD. Model mononuclear model Rh(I) complexes
of the chitosan-supported catalyst were also prepared and
characterized using 1H and 31P NMR, UV-vis and FT-IR
spectroscopy, mass spectrometry, elemental analysis and single
X-ray crystallography.
All the catalysts were active in the hydroformylation of 1-
octene under mild conditions with negligible amounts of Rh
leaching into the solution. The activity as well as regio- and
chemo-selectivity was affected by factors such as temperature
and syngas pressure and under optimal conditions of 75 ◦C
and 30 bar, good selectivity for nonanal was seen for both
the supported and mononuclear catalysts. Iminophosphine-
based catalyst (3) showed the best activity, chemoselectivity,
regioselectivity as well as recyclability and can therefore be
singled out for further development.
12 W.-L. Wei, H.-Y. Zhu, C.-L. Zhao, M.-Y. Huang and Y.-Y. Jiang,
React. Funct. Polym., 2004, 59, 33.
13 M. J. Gronnow, R. Luque, D. J. Macquarrie and J. H. Clark, Green
Chem., 2005, 7, 552.
14 X. Zhang, Y. Geng, B. Han, M.-Y. Ying, M.-Y. Huang and Y. Y.
Jiang, Polym. Adv. Technol., 2001, 12, 642.
15 K. R. Reddy, N. S. Kumar, P. S. Reddy, B. Sreedhar and M/L.
Kantam, J. Mol. Catal. A: Chem., 2006, 252, 12.
16 (a) J. Linden, R. Stoner, K. Knustson, C. Gardner-Hughes, Org.
Disease Control Elicitors, Agro Food Ind. Hi-Te, 2000, pp. 12; (b) S.
F. Ausar, N. Passalacqua, L. F. Castagna, I. D. Bianco and D. M.
Beltramo, Int. Dairy J., 2002, 12, 899; (c) Z. Guo, R. Xing, S. Liu,
Z. Zhang, X. Ji, L. Wang and P. Li, Carbohydr. Res., 2007, 342, 1329;
(d) R.-M. Wang, N.-P. Pe, P.-F. Song, Y.-F. He, L. Ding and Z.-Q.
Lei, Polym. Adv. Technol., 2009, 20, 959; (e) R.-M. Wang, N.-P. Pe,
P.-F. Song, Y.-F. He, L. Ding and Z. Lei, Pure Appl. Chem., 2009, 81,
2397.
17 (a) H. Wang, W. Sun and C. Xia, J. Mol. Catal. A: Chem., 2003, 206,
199; (b) J. E. dos Santos, E. R. Dockal and E. T. G. Cavalheiro, Carb.
Res., 2005, 60, 277.
18 (a) J. J. E. Hardy, S. Hubert, D. J. Macquarrie and A. J. Wilson, Green
Chem., 2004, 6, 53; (b) Y. Cui, L. Zhang, Y. Li and Polym, Polym.
Adv. Technol., 2005, 16, 633; (c) X. Xu, P. Liu, S.-H. Li, P. Zhang
and X.-Y. Wang, React. Kinet. Catal. Lett., 2006, 88, 217; (d) Y. A.
Skorik, C. A. R Gomes, M. T. S. D. Vasconcelos and Y. G. Yatluk,
Carbohydr. Res., 2003, 338, 271.
Acknowledgements
We would like to thank the University of Cape Town, the
National Research Foundation of South Africa and NRF-
DST Centre of Excellence in Catalysis (c*change) for financial
support. A generous loan of rhodium trichloride from the
AngloPlatinum Corporation/ Johnson Matthey is gratefully
acknowledged.
References
1 (a) O. Roelen, US Patent, 2327066, 1943; (b) P. Eibracht, L. Barfacker,
C. Buss, C. Hollmann, B. E. Kistsos-Rzychon, C. L. Kranemann, T.
Rische, R. Roggenbuck and A. Schmidt, Chem. Rev., 1999, 99, 3329
and references therein; (c) B. Cornils, W. A. Herrmann, M. Rasch
and M. Beller, Angew. Chem., Int. Ed. Engl., 1994, 33, 2144; (d) B.
Cornils, C. D. Frohning and C. W. Kohlpaintner, J. Mol. Catal. A:
Chem., 1995, 104, 17; (e) B. Cornils, W. A. Herrmann and R. W.
Ecki, J. Mol. Catal. A: Chem., 1997, 116, 27; D. Evans, J. A. Osborn
and G. Wilkinson, J. Chem. Soc. A, 1968, 13133; (f) P. W. N. M.
van Leeuwen, C. Claver, Rh-Catalyzed Hydroformylation, Kluwer
Academic, Dordrecht, 2000, pp. 6; (g) B. Cornils, W. A. Herrmann
and M. Rasch, ’Otto Roelen, Pioneer in Industrial Homogeneous
346 | Green Chem., 2012, 14, 338–347
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