biostudies-literatureGeng CDeutsche ForschungsgemeinschaftFonds der Chemischen IndustrieNational Natural Science Foundation of China12940-12945https://www.ebi.ac.uk/biostudies/studies/S-EPMC6852486biostudies-literatureUnknown25(56)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 encounChemistry (Weinheim an der Bergstrasse, Germany)A Reaction-Induced Localization of Spin Density Enables Thermal C-H Bond Activation of Methane by Pristine FeC₄.PMC6852486160 18721473070 and 21773085EXC/314-1Geng CLi JWeiske TSchwarz HfalseA Reaction-Induced Localization of Spin Density Enables Thermal C-H Bond Activation of Methane by Pristine FeC₄.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 encoun2019-01-01T00:00:00Z2019 Oct2025-04-22T21:27:44.225Z2020-05-21T19:10:53ZS-EPMC68524863126819310.1002/chem.201902572