SYNTHESIS AND CHARACTERIZATION OF NEW CHIRAL RH(I) COMPLEXES WITH N,N'-, AND N,P-LIGANDS - A STUDY OF ANCHORING ON THE MODIFIED ZEOLITES AND CATALYTIC PROPERTIES OF HETEROGENIZED COMPLEXES

摘要

Novel chiral bidentate N,N'- and N,P- donors and their rhodium complexes were synthesised and characterized. The reactions of [{Rh(COD)Cl}(2)] and [RhCl(PPh(3))(3)] with different prepared chiral ligands: (S)-1-L-2-t-butylaminocarbonylpyrrolidine (la, Ib), (S)-1-L-2-diphenylphosphinomethylpyrrolidine (2a, 2b), (S)-1-L-2-(1-naphthylaminocarbonyl)pyrrolidine (5a, 5b), (S)-1-L-2-(1-naphthylaminomethyl)pyrrolidine (7a, 7b) (a: L = t-butylaminocarbonyl, b: (3-trietoxysilylpropyl)aminocarbonyl) in the presence of a non-coordinating anion (PF6-) gave the cationic tetracoordinate [Rh(L(2))(ligand)][PF6] (L(2) = COD or PPH3). The structures of these complexes were elucidated by elemental analysis, IR spectroscopy and H-1, C-13 and P-31 NMR. measurements. The metal complexes with Ib, 2b, 5b and 7b, were anchored to silica and modified USY-zeolite and Rh-heterogenized complexes were obtained. A comparative study (homogeneous vs. supported) was made for the catalytic activity and selectivity in several organic reactions. [References: 33]