Abstract
Transformation products of the cationic rhodium complex [(1,5-COD)Rh(—)R,R-DIOP]+CF3SO3 – (1) (COD is cycloocta-1,5-diene and DIOP is (±)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane), which were obtained in its reactions with molecular hydrogen, base (NEt3), and solvents in the absence of a substrate, were investigated by 1H and 31P NMR spectroscopy. The solvate complexes [(Solv)2Rh(—)R,R-DIOP]+CF3SO3 –, which were generated from complex 1 in its reaction with molecular hydrogen, underwent destruction of the diphosphine ligand with elimination of benzene and were subjected to oxidation by traces of moisture and oxygen to form the DIOP dioxide complex with RhI. In the absence of hydrogen, complex 1 in solutions produced the diphosphine dioxide rhodium(i) complex and mono- and binuclear rhodium(i) solvate complexes. The scheme of deactivation of the complex in the absence of the substrate was proposed. The catalytic activity of the solvate complexes [(ArH)Rh(—)R,R-DIOP]+CF3SO3 –, which contain benzene, p-xylene, and mesitylene in the coordination sphere, was studied in hydrogenation of Z-α-acetamidocinnamic acid.
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Nindakova, L.O., Shainyan, B.A. Transformations of the chiral diphosphine rhodium catalyst [(1,5-COD)Rh(—)R,R-DIOP]+CF3SO3– under conditions of hydrogenation. Russian Chemical Bulletin 50, 1855–1859 (2001). https://doi.org/10.1023/A:1014338330802
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DOI: https://doi.org/10.1023/A:1014338330802