Novel nucleophilic reactivity of disulfido ligands coordinated parallel to M-M (M = Rh, Ir) bonds

Inorg Chem. 2004 Sep 6;43(18):5688-97. doi: 10.1021/ic049855t.

Abstract

Reaction of trans-[(MCp)(2)(mu-CH(2))(2)Cl(2)] (M = Rh, Ir; Cp = eta(5)-C(5)Me(5)) with Li(2)S(2) afforded the disulfido complexes [(MCp)(2)(mu-CH(2))(2)(mu-S(2)-S:S')] which were easily oxidized by O(2) to give the oxygenated complexes [(MCp)(2)(mu-CH(2))(2)(mu-SSO(2)-S:S')]. Although [(RhCp)(2)(mu-CH(2))(2)(mu-S(2)-S:S')] gave a complicated mixture when reacted with CH(2)Cl(2) or CHCl(3), [(IrCp)(2)(mu-CH(2))(2)(mu-S(2)-S:S')] reacted with both CH(2)Cl(2) and CHCl(3) to give the dithioformato complex [(IrCp)(2)(mu-CH(2))(2)(mu-S(2)CH-S:S')]Cl and the cyclotetrasulfido complex [((IrCp)(2)(mu-CH(2))(2))(2)(mu-S(4)-S:S':S":S"')]Cl(2). The oxygenated complexes [(RhCp)(2)(mu-CH(2))(2)(mu-SSO(2)-S:S')] reacted with hydrocarbyl halides to afford bridging hydrocarbyl thiolato complexes accompanied by the generation of SO(2) gas. These complexes have been characterized by NMR spectroscopy, ESI-MS, and X-ray diffraction.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Disulfides / chemistry*
  • Iridium / chemistry*
  • Ligands
  • Models, Chemical
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Rhodium / chemistry*

Substances

  • Disulfides
  • Ligands
  • Organometallic Compounds
  • Iridium
  • Rhodium