Structure and Reactivity Control of Ambiphilic Oxygen Species

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Structure and reactivity of XOO species as an important active oxygen species have been studies systematically. The characteristic reactivity of XOO species for carbonyl oxides (X = R_2C) and persulfoxides(X = R_2S) is a nucleophilic oxygen transfer to sulfoxides, which suggest that the XOO species are shown as a 1,3-dipolar reagent. In contrast, nitroso oxides (RNOO) transfer oxygen atoms as an electrophilic 1,3-diradical. The cyclization of XOO species to cyclic dioxiranes has been shown not to occur for the cases of carbonyl oxides and persulfoxides, which could be rationalized by the double bond nature of X-O bobd for X = C and S atoms. The cyclization of XOO species was shown to be facile for the case of nitroso oxides (X = N atoms), which reflects the single bond nature of N-O bond of RNOO 1,3-diradicals. The predominant factor controlling the reactivity of XOO species has been shown to be the electronegativity of X.