Dioxetanones%26apos; peroxide bond as a charge-shifted bond: implications in the chemiluminescence process

作者：da Silva Luis Pinto; Esteves da Silva Joaquim C G

来源：Structural Chemistry, 2014, 25(4): 1075-1081.

DOI：10.1007/s11224-013-0383-1

• Firefly dioxetanone
• Charge-shifted bonds
• Chemiluminescence
• Peroxide bond
• Electron localization function
• Quantum theory of atoms in molecules

Six dioxetanone molecules, ranging in complexity from simple dioxetanone to firefly dioxetanone, were studied by performing M06/6-311G(d,p) calculations. The quantum theory of atoms in molecules and the electron localization function was applied to analyze the peroxide and carbon-carbon bonds of the dioxetanone ring. Both approaches demonstrated that the peroxide bond is not covalent, but charge-shifted. This means that for this bond the covalent %26quot;electron sharing%26quot; is relatively unimportant, and it is the stabilizing resonance energy that causes the bonding. For the contrary, the carbon-carbon bond is covalent. These discoveries indicate that no biradical species should be formed in the dioxetanone decomposition, and that the most probable rate-determining step should be the carbon-carbon cleavage.

• 出版日期2014-8