Synthesis, structure, and interconversion of chiral rhenium oxygen- and sulfur-bound sulfoxide complexes of formula [(η 5 -C 5 H 5 )Re(NO)(PPh 3 )(OS(Me)R)] + X − ; diastereoselective oxidations of coordinated methyl alkyl sulfides Academic Article uri icon

abstract

  • Reactions of the chiral chlorobenzene complex [(η5-C5H5)Re(NO)(PPh3) (ClC6H5)]+BF4- (1+ BF4-) and alkyl methyl sulfoxides O=S(Me)R (R = a, Me; b, Et; c, i-Pr or d, t-Bu), at -15°C gave the oxygen-bound sulfoxide complexes [(η5-C5H5)Re(NO)(PPh)3 (O=S(Me)R)]+ BF4- (2a-2d+BF4-; 94-56%). Above 0°C, 2a-2d+BF4- rearrange to sulfur-bound linkage isomers [(η5-C5H5)Re(NO)(PPh3) (S(=O)(Me)R)]+BF4- (3a-3d+BF4-; 96-20%). The triflate salts 2c,2d+TfO- and 3b,3c+TfO- are analogously prepared from (η5-C5H5)Re(NO)(PPh3)(OTf). Complexes 2b-2d+X- and 3b-3d+X- can exist as two Re, S configurational diastereomers. Stereochemistry is assigned from reactions of (S)- or (R)-1+BF4- with enantiomerically enriched sulfoxides (R)-b-d, and a crystal structure of (SReRS,RReSS)-2d+ TfO-·0.5CH2Cl2. Relative diastereomer stabilities, and the basis for the divergent kinetic and thermodynamic oxygen/sulfur binding selectivities, are analysed. The alkyl methyl sulfide complexes [(η5-C5H5)Re(NO)(PPh3) (S(Me)R)]+ X- and dimethyldioxirane react (acetone, -20°C) to give 3a-3d+X-. Diastereoselectivities (3b-3d+X-) are fair to good. However, some overoxidation to Ph3P=O occurs, lowering yields.

author list (cited authors)

  • Otto, M., Boone, B. J., Arif, A. M., & Gladysz, J. A.

citation count

  • 10

publication date

  • January 2001