872415-80-0Relevant academic research and scientific papers
Reactivity studies of iridiuni(III) porphyrins with methanol in alkaline media
Cheung, Chi Wai,Fung, Hong Sang,Lee, Siu Yin,Qian, Ying Ying,Chan, Yun Wai,Chan, Kin Shing
experimental part, p. 1343 - 1354 (2010/05/14)
Ir(ttp)Cl(CO) (la; ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) was found to cleave the C-O bond of CH3OH at 200 C to give Ir(ttp)CH3 (3a). Addition of KOH promoted the reaction rate and gave a higher yield of Ir(ttp)CH3 in 70% yield in 1 day. Mechanistic studies suggest that, in the absence of KOH, Ir(ttp)Cl(CO) reacts with CH 3OH initially to give Ir(ttp)OCH3, which then undergoes β elimination to produce Ir(ttp)H (4a). Ir(ttp)H further reacts slowly to cleave the C-O bond of CH3OH, likely via cr-bond metathesis, to give Ir(ttp)CH3. In the presence of KOH, Ir(ttp)Cl(CO) initially reacts with KOH more rapidly to give Ir(ttp)OH, which then cleaves the 0-H bond of CH3OH by metathesis to give Ir(ttp)OCH3. Ir(ttp)OCH 3 further isomerizes via /3-hydride elimination/reinsertion to give Ir(Up)CH2OH and concurrently undergoes base-assisted /3-proton elimination to give Ir(ttp)-K+ (5a). Ir(ttp)CH.20H subsequently condenses with CH3OH to form. Ir(Up)CH2OCH3 (2). Finally, Ir(ttp)-K+ cleaves the C-O bond in CH3OH, most probably via nucleophilic substitution, to give Ir(ttp)CH3. Ir(ttp)CH 2OCH3 also serves as the precursor of Ir(ttp)-K+ as it undergoes nucleophilic substitution by KOH to give Ir(ttp)-K+.
Base-promoted selective activation of benzylic carbon-hydrogen bonds of toluenes by iridium(III) porphyrin
Cheung, Chi Wai,Chan, Kin Shing
, p. 3043 - 3055 (2009/02/05)
K2CO3 and NaOPh promoted the rate of benzylic carbon-hydrogen bond activation (BnCHA) of toluenes with iridium(III) porphyrin carbonyl chloride (Ir(ttp)Cl(CO)) to give iridium porphyrin benzyls in high yields. Mechanistic studies sug
