title: A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(iii)-PyBisulidine.
abstract: An environmentally friendly new protocol for the selective aerobic cleavage of styrene to carbonyl compounds using the Fe(iii)-PyBisulidine catalyst has been reported recently. The catalyst features several unusual characteristics, such as its high efficiency lies on the ferric center instead of ferrous used by most iron-containing oxygenases and the catalyst specifically oxidizes phenyl-substituted olefins but exhibits no activity on nonconjugated olefins. Herein, we have investigated the mechanism of the oxidative cleavage reaction catalyzed by Fe(iii)-PyBisulidine at the quantum chemistry level. Our computational study shows that the catalyst uses a dioxygen ligation mechanism to activate dioxygen to receive one electron from olefin, which triggers the oxidative cleavage reaction. Our study rationalizes that the Fe(ii)-PyBisulidine catalyst is inactivated because ferrous is unable to raise the oxidizing ability of dioxygen. The exclusive oxidative cleavage of the phenyl-substituted olefin mainly results from the stability of the carbon cation, the orbital symmetry between the conjugated olefin and dioxygen, as well as a lower energy level of HOMO in conjugated olefin.
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, China. hongwei.tan@bnu.edu.cn.
authors.forename: Yafei
authors.identifier: http://orcid.org/0000-0001-7272-8453
authors.initials: Y
authors.lastname: Jiang
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, China. hongwei.tan@bnu.edu.cn.
authors.forename: Xiaotong
authors.identifier: http://orcid.org/0000-0001-8407-4792
authors.initials: X
authors.lastname: Zhang
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, China. hongwei.tan@bnu.edu.cn.
authors.forename: Qiuyun
authors.initials: Q
authors.lastname: Mao
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, China. hongwei.tan@bnu.edu.cn.
authors.forename: Hongwei
authors.identifier: http://orcid.org/0000-0002-1376-6019
authors.initials: H
authors.lastname: Tan
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, China. hongwei.tan@bnu.edu.cn.
authors.forename: Xichen
authors.identifier: http://orcid.org/0000-0002-1643-4327
authors.initials: X
authors.lastname: Li
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, China. hongwei.tan@bnu.edu.cn.
authors.forename: Guangju
authors.initials: G
authors.lastname: Chen
authors.affiliation: Department of Biomedical and Molecular Sciences, Queen's University, Kingston, Ontario, Canada K7N 3L6. jia@queensu.ca.
authors.forename: Zongchao
authors.initials: Z
authors.lastname: Jia