Synchrotron photoionization measurements of OH-initiated cyclohexene oxidation: ring-preserving products in OH + cyclohexene and hydroxycyclohexyl + O2 reactions

J Phys Chem A. 2012 Jun 28;116(25):6720-30. doi: 10.1021/jp3022437. Epub 2012 Jun 18.

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 H(2)O(2) photolysis in the presence of C(6)D(10) 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-d(4) confirms this result and allows mass discrimination of different abstraction pathways. Products of 2-hydroxycyclohexyl-d(10) reaction with O(2) are observed upon adding a large excess of O(2) to the OH + C(6)D(10) system.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Cyclohexanols / chemistry*
  • Cyclohexenes / chemistry*
  • Hydroxyl Radical / chemistry*
  • Mass Spectrometry
  • Molecular Structure
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Photochemical Processes
  • Synchrotrons

Substances

  • Cyclohexanols
  • Cyclohexenes
  • cyclohexene
  • Hydroxyl Radical
  • Oxygen