%0 Journal Article
%A Vereecken, Luc
%T The reaction of Criegee intermediates with acids and enols
%J Physical chemistry, chemical physics
%V 19
%N 42
%@ 1463-9084
%C Cambridge
%I RSC Publ.
%M FZJ-2017-07258
%P 28630-28640
%D 2017
%X The reaction of CH2OO, the smallest carbonyl oxide (Criegee intermediate, CI), with several acids was investigated using the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemical method, as well as microvariational transition state theory and RRKM master equation theoretical kinetic methodologies. For oxoacids HNO3 and HCOOH, a 1,4-insertion mechanism allows for barrierless reactions with high rate coefficients, in agreement with literature experimental data. This mechanism relies on the presence of a double bond in the α-position to the acidic OH group. We predict that reactions of CI with enols will likewise have high rate coefficients, proceeding through a similar mechanism. The hydracid HCl was found to react through a less favorable 1,2-insertion reaction, leading to lower rate coefficients, again in good agreement with the literature. We conclude that the reaction mechanism is the main indicator for the reaction rate for CH2OO + acid reactions, with acidity only of secondary influence. At room temperature and 1 atm the main product for all reactions was found to be the thermalized hydroperoxide initial adduct, with minor yields of fragmentation products. One of the product channels characterized is a novel reaction path involving intramolecular H-abstraction after a roaming reaction in the OH + product radical complex formed by the dissociation of the hydroperoxide adduct; this channel is the lowest fragmentation route for some of the reactions studied.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ pmid:29057418
%U <Go to ISI:>//WOS:000414243300016
%R 10.1039/C7CP05132H
%U https://juser.fz-juelich.de/record/838697