1052191-86-2

Upstream product

• 1052191-72-6 [Ir2(η5-C5Me5)2(μ-bis(dimethylphosphino)methane)(μ-hydrido)](triflate) 
• 108-88-3 toluene 

Relevant 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)]+

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.

Activation of C-H and H-H bonds by dinuclear iridium complexes. Oxidative addition to highly active unsaturated 32e- diiridium species

Reactions of [(Cp*Ir)2(μ-dmpm)(μ-H)2][OTf]2 (1) with NaOtBu in aromatic solvent at room temperature give [(Cp*Ir)(H)(μ-dmpm)(μ-H)(Cp*Ir)(Ar)][OTf] [Ar = Ph (3), p-Tol (4a), m-Tol (4b), 2-furyl (5a), 3-furyl (5b)] via intermolecular aromatic C-H activation. Treatment of [(Cp*Ir)2(μ-dppm)(μ-H)2][OTf]2 (2) with weak base (Et2NH) results in intramolecular C-H activation of a phenyl group in the dppm ligand to give [(Cp*Ir)(H){μ-PPh(C6H4)CH2PPh2}(μ-H)(Cp*Ir)][OTf] (6). Reaction of 1 with NaOtBu in tetrahydrofuran under H2 (1 atm) results in activation of the H-H bond to give [{(Cp*Ir)(H)}2(μ-dmpm)(μ-H)][OTf] (7). Reaction of 1 with NaOtBu in dichloromethane under carbon monoxide (1 atm) gives a carbonyl-bridged IrII-IrII complex, [(Cp*Ir)2(μ-dmpm)(μ-H)(μ-CO)][OTf] (8-OTf). These results strongly suggest that the active species in C-H and H-H bond activation starting with 1 and 2 would be unsaturated 32e- diiridium species. The structures of 3, 5a, 6, 7, and 8-BPh4 have been determined by X-ray diffraction methods.

Inter- and intramolecular activation of aromatic C-H bonds by diphosphine and hydrido-bridged dinuclear iridium complexes

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