absorption coefficient 5 1.635 mm21, reflections collected 5 7324,
independent reflections 5 2804 [ R(int) 5 0.0435], The final wR2 was
b502435h/ for crystallographic data in CIF or other electronic format.
While vinyl acetate and vinyl benzoate also show good
conversions and selectivities, 1-octene reacts well but with no
selectivity. Several functionalized olefins did not react under
these conditions (for example phenyl vinyl sulfone,
N-methylvinylacetamide), while isopropyl vinyl ether and 2,2-
dimethyl-4- vinyl-1,3-dioxolane gave aldehydes in moderate yield
but in quite low selectivity.
1 I. Ojima, C.-Y. Tsai, M. Tzamarioudaki and D. Bonafoux, The
Hydroformylation Reaction, Org. React., 2000, 56, 1–354.
2 D. Evans, J. A. Osborn and G. Wilkinson, J. Chem. Soc. A, 1968, 3133;
P. W. N. M. van Leeuwen and C. Claver, Rhodium Catalyzed
Hydroformylation, Kluwer Academic, Dordrecht, 2000; F. Ungvary,
Coord. Chem. Rev., 2003, 241, 295; V. V. Grushin, Chem. Rev., 2004, 104,
1629.
3 G. D. Cuny and S. L. Buchwald, J. Am. Chem. Soc., 1993, 115, 2066;
K. Nozaki, N. Sakai, T. Nanno, T. Higashijima, S. Mano, T. Horiuchi
and H. Takaya, J. Am. Chem. Soc., 1997, 119, 4413; D. Selent,
K. D. Wiese, D. Ro¨ttger and A. Bo¨rner, Angew. Chem., Int. Ed., 2000, 39,
1639.
4 D. A. Aubry, N. N. Bridges, K. Ezell and G. G. Stanley, J. Am. Chem.
Soc., 2003, 125, 11180; C. Li, E. Widjaja and M. Garland, J. Am. Chem.
Soc., 2003, 125, 5540.
5 I. Amer and H. Alper, J. Am. Chem. Soc., 1990, 112, 3674.
6 P. Frediani, M. Bianchi, A. Salvini, L. C. Carluccio and L. Rosi,
J. Organomet. Chem., 1997, 547, 35.
In conclusion, ionic diamine–rhodium complexes, which have a
chloride localized anionic rhodium and a chlorine free cationic
rhodium center, were synthesized and used as catalysts for the
hydroformylation reaction. These complexes show excellent
activity and regioselectivity without any phosphorus ligand, under
very mild reaction conditions.
We are indebted to Sasol Technology Ltd. for support of this
research.
Jai Jun Kim and Howard Alper*
Centre for Catalysis Research and Innovation, Department of
Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Canada
264125. E-mail: howard.alper@uottawa.ca; Fax: +1 613 562 5871;
Tel: +1 613 562 5189
7 M. A. Garralda and L. Ibarlucea, J. Organomet. Chem., 1986, 311,
225.
8 J. A. Moulijn, P. W. N. M. van Leeuwen and R. A. van Santen,
Catalysis: An Integrated Approach to Homogeneous, Heterogeneous and
Industrial Catalysis, Elsevier, Amsterdam, 1993.
Notes and references
9 B. G. Reuben and H. A. Wittcoff, Pharmaceutical Chemicals in
Perspective, John Wiley, New York, 1989; D. P. Riley, D. P. Getman,
G. R. Beck and R. M. Heintz, J. Org. Chem., 1987, 52, 287.
{ Crystal data. For complex 2: C11H20ClNRh, M 5 304.6, monoclinic,
3
a 5 10.9386(18), b 5 9.6760(16), c 5 11.3108(19), A, U 5 1181.0(3) A ,
˚
˚
T 5 205(2) K, space group P2/n, Z 5 4, b cell angle 5 99.428(3)u,
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Chem. Commun., 2005, 3059–3061 | 3061