(S)-2-Pyridyl-imino-[2.2]paracyclophane ligands 1 and 2 were synthesized by a condensation reaction of 2-COR-C5H4N (1: R = H; 2: R = Me) with enantiopure (-)-S-amino-[2.2]-paracyclophane. The reactions of 1 and 2 with [Ru(mu(6)-cymene)Cl(p-Cl)]2 afforded complexes [Ru(eta(6)-cymene)Cl(N,N)]X (3: N,N = 1; 4: N,N = 2; X- = BPh4-, PF6-, BF4-) that were completely characterized in solution. For 4PF(6) the solid state structure was determined by X-ray single-crystal diffractometric studies. Two diastereoisomers [(S-Ru, S-L) and (R-Ru, S-L)] were obtained in solution due to the presence of the planar chirality of paracyclophane (L) and the central chirality on ruthenium. H-1-NOESY NMR experiments were used to determine the chirality of the metal center and, consequently, to identify (S-Ru, S-L) and (R-Ru, S-L) diastereoisomers. The cymene orientation, obtained by intramolecular 1H-NOESY NMR investigations, and the relative anion-cation position, determined by interionic H-1-NOESY or F-19,H-1-HOESY NMR studies, depended on the nature of the diastereoisomer. (c) 2005 Elsevier B.V. All rights reserved.
Cationic half-sandwich Ru(II) complexes bearing (S)-2-pyridyl-imino-[2.2]paracyclophane ligands: Synthesis, intramolecular and interionic structure
ZUCCACCIA, Daniele;
2006-01-01
Abstract
(S)-2-Pyridyl-imino-[2.2]paracyclophane ligands 1 and 2 were synthesized by a condensation reaction of 2-COR-C5H4N (1: R = H; 2: R = Me) with enantiopure (-)-S-amino-[2.2]-paracyclophane. The reactions of 1 and 2 with [Ru(mu(6)-cymene)Cl(p-Cl)]2 afforded complexes [Ru(eta(6)-cymene)Cl(N,N)]X (3: N,N = 1; 4: N,N = 2; X- = BPh4-, PF6-, BF4-) that were completely characterized in solution. For 4PF(6) the solid state structure was determined by X-ray single-crystal diffractometric studies. Two diastereoisomers [(S-Ru, S-L) and (R-Ru, S-L)] were obtained in solution due to the presence of the planar chirality of paracyclophane (L) and the central chirality on ruthenium. H-1-NOESY NMR experiments were used to determine the chirality of the metal center and, consequently, to identify (S-Ru, S-L) and (R-Ru, S-L) diastereoisomers. The cymene orientation, obtained by intramolecular 1H-NOESY NMR investigations, and the relative anion-cation position, determined by interionic H-1-NOESY or F-19,H-1-HOESY NMR studies, depended on the nature of the diastereoisomer. (c) 2005 Elsevier B.V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
