Optical resolution of π-thiophene complexes (C6Me6)Ru(2-RC4H3S)2+ and related studies

Karen K. Dailey, Thomas B. Rauchfuss

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Diastereomeric iminium thiolato complexes were prepared by the addition of S-(-)-α-methylbenzylamine to the π-thiophene complexes [(C6Me6)Ru(2-RC4H3S)]2+, where R = Me (12+), CH2OH (32+), and 2-C4H3S (62+). After chromatographic separation, the diastereomers were treated with HOTf to generate optically pure π-thiophene complexes. The absolute configuration of [(C6Me6)RuSCMeC2H2(CHNHCHMePh)]OTf, (-)-2(OTf), was determined by a single-crystal X-ray diffraction; the monohydrate crystallized in the acentric space group P212121. Acetone solutions of (-)-12+ and (-)-32+ are optically stable for days in solution (25°C), while the bithiophene complex was unstable with respect to dissociation of the bithiophene ligand. Optical resolution of [(cymene)Os(2-MeC4H3S)](OTf)2 was not possible due to the instability of the iminium thiolato. Base hydrolysis of (-)-12+ gave the formyl thiolato complex (-)-9kin, which isomerized to (+)-9therm with inversion of configuration at Ru, as indicated by circular dichroism measurements. The methyl ester of the amino acid (L)-phenylalanine was shown to add to (C6Me6)Ru(C4H4S)2+ to give a 2:1 mixture of diastereomeric iminium thiolato complexes.

Original languageEnglish (US)
Pages (from-to)858-865
Number of pages8
Issue number5
StatePublished - 1997

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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