Novel, optically pure 2-{4-methyl[2]paracyclo[2](5,8)quinolinophan-2-yl}-4-aryl/alkyloxazolines (QUIPHANOX) exhibiting both planar and central chirality have been prepared by reacting (R-p)- and (S-p)-2-cyano-4-methyl[2]paracyclo[2](5,8)quinolinophane with 2-aryl/alkyl-2-aminoethanols. The reaction of each of the above N,N-ligands with [Ru(eta(6)-p-cymene)Cl-2](2) in methanol, in the presence of either NH4PF6 or NaBPh4, gave the corresponding half-sandwich [(eta(6)-p-cymene)Ru(QUIPHANOX)Cl]Y-+(-), (Y- = PF6-, BPh4-) as stable complex salts exhibiting planar and carbon- and metal-centered chirality. The unknown absolute configuration (AC) at the metal was determined by H-1 NMR and by theoretical calculations of electronic circular dichroism (ECD) spectra and subsequently confirmed by crystallographic X-ray analysis. (R-p) and (S-p)-ligands afforded (R-Ru)- and (S-Ru)-configured complexes, respectively, independent of the AC at the chiral carbon of the oxazoline moiety.
Cationic half-sandwich quinolinophaneoxazoline-based (η6-p-cymene)ruthenium(ii) complexes exhibiting different chirality types: synthesis and structural determination by complementary spectroscopic methods
RUZZICONI, Renzo;BELLACHIOMA, Gianfranco;CIANCALEONI, Gianluca;LEPRI, SUSAN;
2014
Abstract
Novel, optically pure 2-{4-methyl[2]paracyclo[2](5,8)quinolinophan-2-yl}-4-aryl/alkyloxazolines (QUIPHANOX) exhibiting both planar and central chirality have been prepared by reacting (R-p)- and (S-p)-2-cyano-4-methyl[2]paracyclo[2](5,8)quinolinophane with 2-aryl/alkyl-2-aminoethanols. The reaction of each of the above N,N-ligands with [Ru(eta(6)-p-cymene)Cl-2](2) in methanol, in the presence of either NH4PF6 or NaBPh4, gave the corresponding half-sandwich [(eta(6)-p-cymene)Ru(QUIPHANOX)Cl]Y-+(-), (Y- = PF6-, BPh4-) as stable complex salts exhibiting planar and carbon- and metal-centered chirality. The unknown absolute configuration (AC) at the metal was determined by H-1 NMR and by theoretical calculations of electronic circular dichroism (ECD) spectra and subsequently confirmed by crystallographic X-ray analysis. (R-p) and (S-p)-ligands afforded (R-Ru)- and (S-Ru)-configured complexes, respectively, independent of the AC at the chiral carbon of the oxazoline moiety.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
