ENANTIOSELECTIVE OXIDATION OF RACEMIC PHOSPHINES WITH CHIRAL OXORUTHENIUM PORPHYRINS AND CRYSTAL-STRUCTURE OF [5,10,15,20-TETRAKIS[O-((2-METHOXY-2-PHENYL-3,3,3-TRIFLUOROPROPANOYL)AMINO)PHENYL]PORPHYRINATO](CARBONYL)(TETRAHYDROFURAN)RUTHENIUM(II) (ALPHA,BETA,ALPHA,BETA, ISOMER)

The synthesis of dioxoruthenium(VI) picket-fence complexes bearing optically active alpha-methoxy-alpha-(trifluoromethyl)phenylacetyl residues on both sides of the porphyrin plane (alpha,beta,alpha,beta and alpha,alpha,beta,beta isomers) are described. These chiral porphyrins have been characterized by UV-visible, IR, and H-1,C-13, and F-19 NMR spectroscopy. For benzylmethylphenylphosphine a chiral recognition was observed for the oxygen-atom transfer to phosphorus yielding optically active phosphine oxide with 41% enantiomeric excess. A mechanism for phosphine oxidation involving kinetic resolution to give an oxoruthenium(IV) intermediate is proposed. An X-ray crystal structure determination of the Ru(CO) complex of the alpha,beta,alpha,beta isomer was carried out. Crystal data for RuF12O10N8C89H64: M(r) = 1734.6, orthorhombic, P2(1)2(1)2(1), a = 14.481(3) Angstrom, b = 22.729(6) Angstrom, c = 25.491(6) Angstrom, V = 8390(3) Angstrom(-3), Z = 4, D-X = 1.37 Mg m-(3), lambda (Mo K-alpha) = 0.709 26 Angstrom, mu = 2.68 cm(-1), F(000) = 3544, T = 293 K, final R = 0.070 for 4198 observations.