title: C-H activation on a diphosphine and hydrido-bridged diiridium complex: generation and detection of an active IrII-IrII species [(Cp*Ir)2(micro-dmpm)(micro-H)]+.
abstract: Reaction of [Cp*Ir(micro-H)](2) (5) (Cp* = eta(5)-C(5)Me(5)) with bis(dimethylphosphino)methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir)(2)(micro-dmpm)(micro-H)(2)] (3). Treatment of 3 with methyl triflate at -30 degrees C results in the formation of [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Me)(IrCp*)][OTf] (6). Warming a solution of above 0 degrees C brings about predominant generation of 32e(-) Ir(II)-Ir(II) species [(Cp*Ir)(micro-dmpm)(micro-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 degrees C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(micro-Me(2)PCH(2)PMeCH(2))(micro-H)(IrCp*)][OTf] (8), which is formed by intramolecular oxidative addition of the methyl C-H bond of the dmpm ligand. Intermolecular C-H bond activation reactions with 7 are also examined. Reactions of 7 with aromatic molecules (benzene, toluene, furan, and pyridine) at room temperature result in the smooth sp(2) C-H activation to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H)(micro-dmpm)(micro-C(5)H(4)N)(H)(IrCp*)][OTf] (12), respectively. Complex also reacts with cyclopentene at 0 degrees C to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis.
authors.affiliation: Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan. yama@kagaku.mbox.media.kyoto-u.ac.jp.
authors.forename: Yoshinori
authors.initials: Y
authors.lastname: Takahashi
authors.forename: Mitsuru
authors.initials: M
authors.lastname: Nonogawa
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Fujita
authors.forename: Ryohei
authors.initials: R
authors.lastname: Yamaguchi
mesh_terms: D002244:Carbon / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D008024:Ligands; D008698:Mesylates / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*
chemical_list: D008024:Ligands; D008698:Mesylates; D009942:Organometallic Compounds; D010720:Phosphines; C078465:methyl triflate; D007495:Iridium; D002244:Carbon; D006859:Hydrogen