title: Novel nucleophilic reactivity of disulfido ligands coordinated parallel to M-M (M = Rh, Ir) bonds.
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.
authors.affiliation: Department of Material Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan. nishioka@sci.osaka-cu.ac.jp
authors.forename: Takanori
authors.initials: T
authors.lastname: Nishioka
authors.forename: Hiroaki
authors.initials: H
authors.lastname: Kitayama
authors.forename: Brian K
authors.initials: BK
authors.lastname: Breedlove
authors.forename: Kimie
authors.initials: K
authors.lastname: Shiomi
authors.forename: Isamu
authors.initials: I
authors.lastname: Kinoshita
authors.forename: Kiyoshi
authors.initials: K
authors.lastname: Isobe
mesh_terms: D004220:Disulfides / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D004220:Disulfides; D008024:Ligands; D009942:Organometallic Compounds; D007495:Iridium; D012238:Rhodium