On the Origin of the Distinctly Different Reactivity of Ruthenium in [MO]+ /CH4 Systems (M=Fe, Ru, Os).
Xiaoyan SunShaodong ZhouLei YueMaria SchlangenHelmut SchwarzPublished in: Angewandte Chemie (International ed. in English) (2018)
The thermal gas-phase reactions of [RuO]+ with methane have been explored by FT-ICR mass spectrometry and high-level quantum-chemical calculations. In contrast to the previously studied [FeO]+ /CH4 and [OsO]+ /CH4 couples, which undergo oxygen/hydrogen atom transfers and dehydrogenation, respectively, the [RuO]+ /CH4 system produces selectively [Ru(CH)2 ]+ and H2 O, albeit with much lower efficiency. Various mechanistic scenarios were uncovered, and the associated electronic origins were revealed by high-level quantum-chemical calculations. The reactivity differences observed for the [MO]+ /CH4 couples (M=Fe, Ru, Os) are due to the subtle interplay of the spin-orbit coupling efficiency, orbital overlap, and relativistic effects.
Keyphrases
- room temperature
- molecular dynamics
- density functional theory
- mass spectrometry
- energy transfer
- ionic liquid
- molecular dynamics simulations
- magnetic resonance
- monte carlo
- climate change
- magnetic resonance imaging
- liquid chromatography
- high resolution
- simultaneous determination
- high performance liquid chromatography
- visible light
- tandem mass spectrometry
- electron transfer