Linkage isomerism of (diamine)platinum(II) complexes of sulfur-containing ylidenemalonate ligands

Kwan Mook Kim, Moo Jin Jun, Youn Soo Sohn

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8 Scopus citations

Abstract

A 1H NMR study has been carried out on (diamine)platinum(II) complexes of 1,3-dithian-2-ylidenemalonate (DTAYM) and 1,3-dithiepane-2-ylidenemalonate (DTEYM) ligands as anionic leaving group in aqueous solution. Only the O,S-chelated isomer was observed in solution for all the DTAYM complexes regardless of the kind of carrier ligand amine as was in the solid state. However, both O,S- and S,S′-chelated isomers were observed in solution for DTEYM complexes, which show linkage isomerism from the O,S-chelate to the thermodynamically more stable S,S′-chelate. The rate of linkage isomerism of the DTEYM complexes was found to be dependent on their amine co-ligands. Molecular dynamics of the DTAYM complexes was also discussed based on their temperature-dependent NMR spectra. The crystal structure of the S,S′-isomer of (NH3)2Pt(DTEYM) · H2O was determined whereas that of the O,S-isomer could not be obtained due to its poor crystallinity.

Original languageEnglish
Pages (from-to)3705-3711
Number of pages7
JournalPolyhedron
Volume16
Issue number21
DOIs
StatePublished - 1997

Keywords

  • (diamine)platinum(II)
  • 1,3-dithian-2-ylidenemalonate
  • 1,3-dithiepane-2-ylidenemalonate
  • Linkage isomerism
  • O,S-chelate
  • S,S′-chelate

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