Base-Promoted Selective Aryl C-Cl Cleavage by Iridium(III) Porphyrins via a Metalloradical Ipso Addition-Elimination Mechanism
Publication in refereed journal

香港中文大學研究人員

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摘要Base-promoted aryl carbon-chlorine bond (Ar-Cl) cleavage by iridium(III) porphyrin carbonyl chloride (Ir(III)(ttp)(CO)Cl; ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) was achieved in the presence of K(2)CO(3) to give iridium(III) porphyrin aryls (Ir(III)(ttp)Ar). Mechanistic studies revealed that K(2)CO(3) promotes the reduction of Ir(ttp)(CO)Cl to give the iridium(II) porphyrin dimer intermediate [Ir(II)(ttp)](2). [Ir(ttp)](2) is the source of Ir(II)(ttp) metalloradical, which cleaves Ar-Cl to give Ir(ttp)Ar and a chlorine radical (Cl(center dot)) via radical ipso substitution in an addition-elimination pathway. Cl(center dot) reacts with [Ir(ttp)](2) to yield Ir(ttp)Cl for subsequent base-promoted reduction and Ir(ttp) for radical chain propagation. Additionally, the base-promoted Ar-Cl cleavage of chlorobenzene (PhCl)by Ir(ttp)(CO)Cl gives both Ir(ttp)Ph and 1,4-bis-iridium(III)-porphyrin benzene, Ir(III)(ttp)(p-C(6)H(4))Ir(III)(ttp). The reactive Cl(center dot) can simultaneously react with PhCl via homolytic aromatic substitution to give 1,4-dichlorobenzene, which further undergoes double Ar-Cl cleavage to form Ir(ttp)(p-C(6)H(4))Ir(ttp).
著者Cheung CW, Chan KS
期刊名稱Organometallics
詳細描述.
出版年份2011
月份9
日期26
卷號30
期次18
出版社AMER CHEMICAL SOC
頁次4999 - 5009
國際標準期刊號0276-7333
電子國際標準期刊號1520-6041
語言英式英語
Web of Science 學科類別Chemistry; Chemistry, Inorganic & Nuclear; CHEMISTRY, INORGANIC & NUCLEAR; Chemistry, Organic; CHEMISTRY, ORGANIC

上次更新時間 2021-26-01 於 01:51