title: User-friendly aerobic reductive alkylation of iridium(III) porphyrin chloride with potassium hydroxide: scope and mechanism.
abstract: Alkylation of iridium 5,10,15,20-tetrakistolylporphyrinato carbonyl chloride, Ir(ttp)Cl(CO) (1), with 1°, 2° alkyl halides was achieved to give (ttp)Ir-alkyls in good yields under air and water compatible conditions by utilizing KOH as the cheap reducing agent. The reaction rate followed the order: RCl < RBr < RI (R = alkyl), and suggests an SN2 pathway by [Ir(I)(ttp)](-). Ir(ttp)-adamantyl was obtained under N2 when 1-bromoadamantane was utilized, which could only undergo bromine atom transfer pathway. Mechanistic investigations reveal a substrate dependent pathway of SN2 or halogen atom transfer.
authors.affiliation: Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, People's Republic of China. ksc@cuhk.edu.hk.
authors.forename: Huiping
authors.initials: H
authors.lastname: Zuo
authors.forename: Zhipeng
authors.initials: Z
authors.lastname: Liu
authors.forename: Wu
authors.initials: W
authors.lastname: Yang
authors.forename: Zhikuan
authors.initials: Z
authors.lastname: Zhou
authors.forename: Kin Shing
authors.initials: KS
authors.lastname: Chan