Two kinds of new optically active chelating ligands bearing a chiral sulfinyl functionality, namely the 3,4-bis-(p-tolylsulfinyl)hexanes 4 and the N-mono- and N,N-disubstituted β-p-tolylsulfinyl ethylamines 5 and 2, have been synthesized and their coordination chemistry with Pd(II) and Rh(I) metals has been studied in detail. Complexes formed with ligands 4 featured a homocoordination between the two sulfur donors and the metal atom, in solution as well as in the solid state, as demonstrated by X-ray diffraction of cis-dichloro[3,4-bis-(p-tolylsulfinyl)hexane]palladium(II) ((3R,4R,RS,RS)-7), in which the ligand shows a C2 symmetry. Complexes formed with ligands 2 and 5 showed a heterocoordination of the metal by the sulfur and the nitrogen donors, as confirmed by X-ray diffraction of cis-dichloro[N,N-dimethyl-2-(p-tolylsulfinyl)ethylamine]palladium(II) ((R)-6). All nine complexes 6−11, displaying a monomeric structure, have been synthesized and completely characterized in the solid state (IR, MS-FAB) as well as in solution (1H and 13C NMR, [α]25D).

Synthesis and structural investigations of novel palladium(II) and rhodium(I) complexes containing chiral ligands with a stereogenic sulfur donor, such as beta-amino sulfoxides and C-2-symmetric bis-sulfoxides

PETTINARI, Claudio;PELLEI, Maura;
1999

Abstract

Two kinds of new optically active chelating ligands bearing a chiral sulfinyl functionality, namely the 3,4-bis-(p-tolylsulfinyl)hexanes 4 and the N-mono- and N,N-disubstituted β-p-tolylsulfinyl ethylamines 5 and 2, have been synthesized and their coordination chemistry with Pd(II) and Rh(I) metals has been studied in detail. Complexes formed with ligands 4 featured a homocoordination between the two sulfur donors and the metal atom, in solution as well as in the solid state, as demonstrated by X-ray diffraction of cis-dichloro[3,4-bis-(p-tolylsulfinyl)hexane]palladium(II) ((3R,4R,RS,RS)-7), in which the ligand shows a C2 symmetry. Complexes formed with ligands 2 and 5 showed a heterocoordination of the metal by the sulfur and the nitrogen donors, as confirmed by X-ray diffraction of cis-dichloro[N,N-dimethyl-2-(p-tolylsulfinyl)ethylamine]palladium(II) ((R)-6). All nine complexes 6−11, displaying a monomeric structure, have been synthesized and completely characterized in the solid state (IR, MS-FAB) as well as in solution (1H and 13C NMR, [α]25D).
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11581/114312
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