1215770-23-2Relevant articles and documents
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
, 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+.