RESUMEN

Chiral-at-metal compounds (R Ru,S C)/(S Ru,S C)-[CyRu(1O-2N)PPh3]PF6 and (R Ru,S C)/(S Ru,S C)-[CyRu(2O-1N)PPh3]PF6 were prepared using anions 1O-2N- and 2O-1N- of the Schiff bases, derived from the hydroxynaphthaldehydes and (S)-1-phenylethylamine. The pure (R Ru,S C)-diastereomers were obtained by crystallization. In the unit cell of (R Ru,S C)-[CyRu(1O-2N)PPh3]PF6, there are three independent molecules, which differ in the propeller sense of the PPh3 ligand. Molecules [1] and [2] have (M PPh3 )-configuration and molecule [3] has (P PPh3 )-PPh3 configuration. PPh3 diastereoisomerism is discussed including other pairs of compounds, differing only in the PPh3 configuration. A conformational analysis reveals an internal stabilization inside the PPh3 ligand by a system of attractive CH/π interactions and a new bonding motif PhPPh3 face-on π-Ar, both characteristic features of [(π-Ar)LL'MPPh3] compounds. The propeller diastereomers interconvert via a low-energy pathway and a high-energy pathway, corroborated by density functional theory calculations.