title: Visible light promoted hydroxylation of a Si-C(sp3) bond catalyzed by rhodium porphyrins in water.
abstract: Catalytic activation of an unstrained, unactivated Si-C(sp(3)) bond in water to form methane and silanol by electrophilic rhodium(III) porphyrin [(por)Rh(III)] in acidic aqueous solutions under visible light (λ ≥ 420 nm) has been developed. Activation of the Si-C(sp(3)) bond occurs through direct Si-C bond cleavage, with methyl group transfer to rhodium to give a porphyrin rhodium methyl complex. Photolysis of (por)Rh-CH(3) in water yields methyl radical and (por)Rh(II). Subsequently, (por)Rh(II) reacts with water rapidly to produce (por)Rh-H and (por)Rh-OH. (por)Rh-OH is then protonated to regenerate (por)Rh(III)-OH(2), and (por)Rh-H undergoes hydrogen atom abstraction by methyl radical to form the observed methane.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
authors.forename: Mengmeng
authors.initials: M
authors.lastname: Yu
authors.forename: Xuefeng
authors.initials: X
authors.lastname: Fu