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

Takanori Nishioka, Hiroaki Kitayama, Brian K. Breedlove, Kimie Shiomi, Isamu Kinoshita, Kiyoshi Isobe

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

Reaction of trans-[(MCp*)2(μ-CH2) 2Cl2] (M = Rh, Ir; Cp* = η5-C 5Me5) with Li2S2 afforded the disulfido complexes [(MCp*)2(μ-CH2) 2(μ-S2-S:S′)] which were easily oxidized by O2 to give the oxygenated complexes [(MCp*)2-(μ- CH2)2(μ-SSO2-S:S′)]. Although [(RhCp*)2(μ-CH2)2(μ-S 2-S:S′)] gave a complicated mixture when reacted with CH 2Cl2 or CHCl3, [(IrCp*) 2(μ-CH2)2(μ-S2-S:S′)] reacted with both CH2Cl2 and CHCl3 to give the dithioformato complex [(IrCp*)2(μ-CH2) 2(μ-S2CH-S:S′)]Cl and the cyclotetrasulfido complex [{(IrCp*)2(μ-CH2)2} 2(μ-S4-S:S′:S″:S‴)]Cl2. The oxygenated complexes [(RhCp*)2(μ-CH2) 2(μ-SSO2-S:S′)] reacted with hydrocarbyl halides to afford bridging hydrocarbyl thiolato complexes accompanied by the generation of SO2 gas. These complexes have been characterized by NMR spectroscopy, ESI-MS, and X-ray diffraction.

Original languageEnglish
Pages (from-to)5688-5697
Number of pages10
JournalInorganic chemistry
Volume43
Issue number18
DOIs
Publication statusPublished - 2004 Sep 6

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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