Dioxetanones' peroxide bond as a charge-shifted bond: implications in the chemiluminescence process

• Type: Article in International Scientific Journal
• Date: 2014

Authors

Luis Pinto da Silva (Author) Other; Joaquim C G E Esteves da Silva (Author) FCUP

Journal

Title: Structural Chemistry

Vol. 25

Pages: 1075-1081

ISSN: 1040-0400

Publisher: Springer Nature

Indexing

ISI Web of Knowledge - 6 Citations

Scopus - 6 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-009-MR7

DOI: 10.1007/s11224-013-0383-1

Abstract (EN): 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 "electron sharing" 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.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 7