620178-86-1Relevant academic research and scientific papers
C-H activation on a diphosphine and hydrido-bridged diiridium complex: Generation and detection of an active IrII-IrII species [(Cp*Ir)2(μ-dmpm)(μ-H)]+
Takahashi, Yoshinori,Nonogawa, Mitsuru,Fujita, Ken-Ichi,Yamaguchi, Ryohei
, p. 3546 - 3552 (2008/12/22)
Reaction of [Cp*Ir(μ-H)]2 (5) (Cp* = η5-C5Me5) with bis(dimethylphosphino) methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir) 2(μ-dmpm)(μ-H)2] (3). Treatment of 3 with methyl triflate at -30 °C results in the formation of [(Cp*Ir)(H)(μ-dmpm) (μ-H)(Me)(IrCp*)][OTf] (6). Warming a solution of 6 above 0 °C brings about predominant generation of 32e- IrII-Ir II species [(Cp*Ir)(μ-dmpm)(μ-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 °C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(μ-Me 2PCH2PMeCH2)(μ-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 sp2 C-H activation to give [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H) (μ-dmpm)(μ-C5H4N)(H)(IrCp*)][OTf] (12), respectively. Complex 7 also reacts with cyclopentene at 0 °C to give [(Cp*Ir)(H)(μ-dmpm)(μ-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis.
Inter- and intramolecular activation of aromatic C-H bonds by diphosphine and hydrido-bridged dinuclear iridium complexes
Fujita, Ken-Ichi,Nakaguma, Hirohide,Hamada, Taro,Yamaguchi, Ryohei
, p. 12368 - 12369 (2007/10/03)
Reactions of [(Cp*Ir)2(μ-dmpm)(μ-H)2]2+ (1) with NaOtBu in aromatic solvent at room temperature give [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Cp*Ir)(Ar)]+ [Ar = Ph (3), p-Tol (4a), m-Tol (4b), 2-furanyl (5a), 3-furan
