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  • Using distonic radical ions to probe the chemistry of key combustion intermediates: the case of the benzoxyl radical anion.

Using distonic radical ions to probe the chemistry of key combustion intermediates: the case of the benzoxyl radical anion.

Journal of the American Society for Mass Spectrometry (2013-03-21)
Cong Li, Adrian K Y Lam, George N Khairallah, Jonathan M White, Richard A J O'Hair, Gabriel da Silva
ABSTRACT

The benzoxyl radical is a key intermediate in the combustion of toluene and other aromatic hydrocarbons, yet relatively little experimental work has been performed on this species. Here, a combination of electrospray ionization (ESI), multistage mass spectrometry experiments, and density functional theory (DFT) calculations are used to examine the formation and fragmentation of a benzoxyl (benzyloxyl) distonic radical anion. Excited 4-carboxylatobenzoxyl radical anions were produced via two methods: (1) collision induced dissociation (CID) of the nitrate ester 4-(nitrooxymethyl)benzoate, (-)O2CC6H4CH2ONO2, and (2) reaction of ozone with the 4-carboxylatobenzyl radical anion, (-)O2CC6H4CH2(•). In neither case was the stabilized (-)O2CC6H4CH2O(•) radical anion intermediate detected. Instead, dissociation products at m/z 121 and 149 were observed. These products are attributed to benzaldehyde (O2(-)CC6H4CHO) and benzene ((-)O2CC6H5) products from respective loss of H and HCO radicals in the vibrationally excited benzoxyl intermediate. In no experiments was a product at m/z 120 (i.e., (-)O2CC6H4(•)) detected, corresponding to absence of the commonly assumed phenyl radical + CH2=O channel. The results reported suggest that distonic ions are useful surrogates for reactive intermediates formed in combustion chemistry.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Benzoyl chloride, SAJ first grade, ≥98.0%
Sigma-Aldrich
Benzoyl chloride, 99%
Sigma-Aldrich
Benzoyl chloride, ReagentPlus®, ≥99%