Synchrotron Photoionization Measurements of OH-Initiated Cyclohexene Oxidation: Ring-Preserving Products in OH + Cyclohexene and Hydroxycyclohexyl + O2 Reactions

Authors:
Publisher website
Google Scholar
Abstract
Earlier synchrotron photoionization mass spectrometry experiments suggested a prominent ring-opening channel in the OH-initiated oxidation of cyclohexene, based on comparison of product photoionization spectra with calculated spectra of possible isomers. The present work re-examines the OH + cyclohexene reaction, measuring the isomeric products of OH-initiated oxidation of partially and fully deuterated cyclohexene. In particular, the directly measured photoionization spectrum of 2-cyclohexen-1-ol differs substantially from the previously calculated Franck–Condon envelope, and the product spectrum can be fit with no contribution from ring-opening. Measurements of H2O2 photolysis in the presence of C6D10 establish that the addition–elimination product incorporates the hydrogen atom from the hydroxyl radical reactant and loses a hydrogen (a D atom in this case) from the ring. Investigation of OH + cyclohexene-4,4,5,5-d4 confirms this result and allows mass discrimination of different abstraction pathways. Products of 2-hydroxycyclohexyl-d10 reaction with O2 are observed upon adding a large excess of O2 to the OH + C6D10 system.

This publication has 47 references indexed in Scilit: