A Reaction-Induced Localization of Spin Density Enables Thermal C-H Bond Activation of Methane by Pristine FeC₄.

ABSTRACT: The reactivity of the cationic metal-carbon cluster FeC₄ ⁺ towards methane has been studied experimentally using Fourier-transform ion cyclotron resonance mass spectrometry and computationally by high-level quantum chemical calculations. At room temperature, FeC₄ H⁺ is formed as the main ionic product, and the experimental findings are substantiated by labeling experiments. According to extensive quantum chemical calculations, the C-H bond activation step proceeds through a radical-based hydrogen-atom transfer (HAT) mechanism. This finding is quite unexpected because the initial spin density at the terminal carbon atom of FeC₄ ⁺ , which serves as the hydrogen acceptor site, is low. However, in the course of forming an encoun

SUBMITTER: Geng C 

PROVIDER: S-EPMC6852486 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature