Gladiali, Serafino Gabriele and Grepioni, Fabrizia and Medici, Serenella and Zucca, Antonio and Berente, Zoltán and Kollar, László (2003) Chiral complexes of RhI containing binaphthalene-core P,S-heterobidentate ligands: synthesis, characterization, and catalytic activity in asymmetric hydrogenation of α,β-unsaturated acids and esters. European Journal of Inorganic Chemistry, Vol. 2003 (3), p. 556-561. eISSN 1099-0682. Article.
Full text not available from this repository.
The enantiopure complexes 3a and 3b [Rh(NBD)(P,S)]+BF4− [P,S = (S)-2-(diphenylphosphanyl)-2′-(methylthio)-1,1′-binaphthalene (a); (S)-2-(diphenylphosphanyl)-2′-(isopropylthio)-1,1′-binaphthalene (b)] have been prepared from [Rh(NBD)(THF)2]+BF4− by reaction with a stoichiometric amount of the appropriate P,S-heterobidentate ligand. Single-crystal X-ray analysis of the S-methyl derivative shows that the seven-membered chelate ring is locked in a boat-like conformation with the methyl group in the equatorial position. Variable-temperature NMR measurements confirm that this conformation is maintained in solution and that the dynamic behaviour displayed by the complex is due to pseudo-rotation of the diolefin. Complexes 3 have been tested in the asymmetric hydrogenation of α,β-unsaturated acids and esters. Enantioselectivities of up to 60% ee have been recorded.
I documenti depositati in UnissResearch sono protetti dalle leggi che regolano il diritto d'autore
Repository Staff Only: item control page