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Alkyl Carbon–Oxygen Bond Cleavage of Aryl Alkyl Ethers by Iridium–Porphyrin and Rhodium–Porphyrin Complexes in Alkaline Media
Organometallics ( IF 2.5 ) Pub Date : 2017-09-11 00:00:00 , DOI: 10.1021/acs.organomet.7b00386 Chen Chen 1 , Kin Shing Chan 1
Organometallics ( IF 2.5 ) Pub Date : 2017-09-11 00:00:00 , DOI: 10.1021/acs.organomet.7b00386 Chen Chen 1 , Kin Shing Chan 1
Affiliation
Alkyl C–O bond cleavage in aryl alkyl ethers was achieved with Rh(ttp)Cl (1a; ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) together with competitive alkyl C–H bond activation in alkaline media. In contrast, selective alkyl C–O bond cleavage occurred with the iridium–porphyrin Ir(ttp)(CO)Cl (1b)/KOH. Mechanistic investigations indicate the coexistence of MI(ttp)− and M2II(ttp)2 (M = Rh, Ir) under basic conditions. With a weaker Rh(ttp)–Rh(ttp) bond, RhII(ttp)· metalloradical exists in an appreciable amount to cleave the alkyl C–H bond, competing with the alkyl C–O bond cleavage via RhI(ttp)−. In contrast, the more nucleophilic IrI(ttp)− cleaves the alkyl C–O bond exclusively.
中文翻译:
铱-卟啉和铑-卟啉配合物在碱性介质中对芳烷基醚的烷基碳氧键的裂解
用Rh(ttp)Cl(1a ; ttp = 5,10,15,20-四(对甲苯基)卟啉对二价阴离子)在烷基烷基中进行烷基C–O键裂解,并在C3中活化烷基C–H键。碱性介质。相反,铱-卟啉Ir(ttp)(CO)Cl(1b)/ KOH发生选择性的烷基C-O键裂解。机理研究表明在基本条件下M I(ttp)-和M 2 II(ttp)2(M = Rh,Ir)共存。由于Rh(ttp)–Rh(ttp)键较弱,Rh II(ttp)·金属铁的存在量足以裂解烷基C–H键,与通过Rh I裂解的烷基C–O键竞争(ttp)-。相比之下,亲核性更高的Ir I(ttp)-仅能裂解烷基C-O键。
更新日期:2017-09-11
中文翻译:
铱-卟啉和铑-卟啉配合物在碱性介质中对芳烷基醚的烷基碳氧键的裂解
用Rh(ttp)Cl(1a ; ttp = 5,10,15,20-四(对甲苯基)卟啉对二价阴离子)在烷基烷基中进行烷基C–O键裂解,并在C3中活化烷基C–H键。碱性介质。相反,铱-卟啉Ir(ttp)(CO)Cl(1b)/ KOH发生选择性的烷基C-O键裂解。机理研究表明在基本条件下M I(ttp)-和M 2 II(ttp)2(M = Rh,Ir)共存。由于Rh(ttp)–Rh(ttp)键较弱,Rh II(ttp)·金属铁的存在量足以裂解烷基C–H键,与通过Rh I裂解的烷基C–O键竞争(ttp)-。相比之下,亲核性更高的Ir I(ttp)-仅能裂解烷基C-O键。