Abstract
Addition of the dithioethers (−)-DIOSR 2 (R=Me, iPr) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD) 2]ClO 4 (COD=1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR 2)]ClO 4. X-ray diffraction methods showed that the [Rh(COD)(DIOS iPr 2)]ClO 4 complex had an square-planar coordination geometry at the rhodium atom with the iPr groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO) 2Rh( μ-DIOSR 2) 2(CO) 2](ClO 4) 2. [Rh(COD)(DIOSR 2)]ClO 4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65°C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low.
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