Probing the cyclic transition state in the reaction O(3P)+alkyl iodides to form HOI: electronic, steric and thermodynamic factors influencing the reaction pathway

The direct production of CO(v=1–9) in the reaction of O(3P) with the ethyl radical

“…We recently implemented a commercial step-scan interferometer in our laboratory for the acquisition of time-resolved interferograms from vibrationally excited molecules. 17 For detection in the infrared we can acquire a time-resolved history of the emitting molecules with a time resolution of ϳ2 s and a spectral resolution of 0.11 cm Ϫ1 . Details of the experimental technique are given in our previous publications and only a concise description is presented here.…”

“…Details of the experimental technique are given in our previous publications and only a concise description is presented here. 17 The reaction is initiated by simultaneous dissociation of SO 2 and either diethyl ketone or ethyl iodide by an ArF 193.3 nm excimer laser with an energy of ϳ100 mJ/pulse, triggered by the FTIR spectrometer after the moving mirror of the interferometer has been stabilized at an interferogram position. The laser pulse permits the time-resolved history of the product species to be attained by defining a reaction initiation time, tϭ0 s. Cylindrical lenses are used to bring the ArF laser beam to a collimated profile of 5 mmϫ5 mm in the reagent flow region.…”

Temperature Dependence Kinetic Studies of the Reaction of O(3P) with CHI3 and C2H5I and the 298 K Reaction of OH(X2Π) with CHI3

“…The reactions of O( 3 P) with alkyl iodides have multipath product channels and have been suggested to proceed via a formation of a R–I–O complex . It has been proposed that the IO elimination is the most important product channel for the short‐chain alkyl iodides, namely, CH 3 I.…”

“…However, the O( 3 P) attack at the β‐position C–H bond in the longer chain alkyl iodides has been suggested to favor the intramolecular H‐atom abstraction via a five‐member transition state to eliminate HOI (see Fig. ) .…”

A kinetic study of the reaction of atomic hydrogen with iodobenzene

“…Interesting kinetics have been observed in some cases, such as Cl-atom addition [9] and O-atom addition followed by elimination of HOI [10]. Rather less attention has been paid to aryl iodides, which are of fundamental interest because they exhibit a range of mechanisms in radical reactions.…”