Details

Autor(en) / Beteiligte

• Vansco, Michael F.
• Zou, Meijun
• Antonov, Ivan O.
• Ramasesha, Krupa
• Rotavera, Brandon
• Osborn, David L.
• Georgievskii, Yuri
• Percival, Carl J.
• Klippenstein, Stephen J.
• Taatjes, Craig A.
• Lester, Marsha I.
• Caravan, Rebecca L.

Titel

Dramatic Conformer-Dependent Reactivity of the Acetaldehyde Oxide Criegee Intermediate with Dimethylamine Via a 1,2-Insertion Mechanism

Ist Teil von

• The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2021-12, Vol.126 (5)

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2021

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The reactivity of carbonyl oxides has previously been shown to exhibit strong conformer and substituent dependencies. Through a combination of synchrotron multiplexed photoionization mass spectrometry experiments (298 K, 4 Torr) and high-level theory (CCSD(T)-F12/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ with an added CCSDT(Q) correction), we explore the conformer dependence of the reaction of acetaldehyde oxide (CH3CHOO) with dimethyl amine (DMA). The experimental data supports the theoretically predicted 1,2-insertion mechanism and the formation of an amine-functionalized hydroperoxide reaction product. Tunable-VUV photoionization probing of anti- or anti- + syn-CH3CHOO reveals a strong conformer dependence of the title reaction. Here, the rate coefficient of DMA with anti-CH3CHOO is predicted to exceed that for the reaction with syn-CH3CHOO by a factor of ~34,000, which is attributed to submerged barrier (syn) vs. barrierless (anti) mechanisms for energetically downhill reactions.