A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(iii)-PyBisulidine.

摘要: An environmentally friendly new protocol for the selective aerobic cleavage of styrene to carbonyl compounds using Fe(iii)-PyBisulidine catalyst has been reported recently. The features several unusual characteristics, such as its high efficiency lies on ferric center instead ferrous used by most iron-containing oxygenases and specifically oxidizes phenyl-substituted olefins but exhibits no activity nonconjugated olefins. Herein, we have investigated mechanism oxidative reaction catalyzed at quantum chemistry level. Our computational study shows that uses a dioxygen ligation activate receive one electron from olefin, which triggers reaction. rationalizes Fe(ii)-PyBisulidine is inactivated because unable raise oxidizing ability dioxygen. exclusive olefin mainly results stability carbon cation, orbital symmetry between conjugated dioxygen, well lower energy level HOMO in olefin.