A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(iii)-PyBisulidine. Issue 12 (2nd March 2017)

• Record Type: Journal Article
• Authors: Jiang, Yafei; Zhang, Xiaotong; Mao, Qiuyun; Tan, Hongwei; Li, Xichen; Chen, Guangju; Jia, Zongchao
• Is Part Of: Dalton transactions. Volume 46:Issue 12(2017)
• Page Start: 3825
• Page End: 3832
• Publication Date: 2017-03-02
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt00229g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The oxidative cleavage of olefins to carbonyls catalyzed by the Fe(iii )-PyBisulidine catalyst was investigated by DFT calculations. 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.