Spin-Selective, Competitive Hydrogen-Atom Transfer versus CH2 O-Generation from the CH4 /[ReO4 ]+ Couple at Ambient Conditions.
Shaodong ZhouMaria SchlangenHelmut SchwarzPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2017)
The thermal gas-phase reactions of [ReO4 ]+ with methane have been explored by using Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. Upon reacting with methane, this cluster oxide, having an even-number of valence electrons, brings about both hydrogen-atom abstraction (HAT) to generate [ReO4 H].+ and the formation of formaldehyde. Mechanistically, HAT occurs on the ground-state triplet surface, while for the generation of formaldehyde a two-state reactivity scenario prevails. The branching ratio of these competing processes is affected by the rather inefficient spin-orbit coupling to bring about the required triplet-singlet intersystem crossing.
Keyphrases
- room temperature
- energy transfer
- molecular dynamics
- mass spectrometry
- density functional theory
- anaerobic digestion
- ionic liquid
- quantum dots
- electron transfer
- air pollution
- particulate matter
- liquid chromatography
- carbon dioxide
- high resolution
- gas chromatography
- molecular dynamics simulations
- visible light
- capillary electrophoresis
- monte carlo
- tandem mass spectrometry