Quadruple C-H Bond Activations of Methane by Dinuclear Rhodium Carbide Cation [Rh₂C₃].

ABSTRACT: The structure of the [Rh₂C₃]⁺ ion and its reaction with CH₄ in the gas phase have been studied by infrared photodissociation spectroscopy and mass spectrometry in conjunction with quantum chemical calculations. The [Rh₂C₃]⁺ ion is characterized to have an unsymmetrical linear [Rh-C-C-C-Rh]⁺ structure existing in two nearly isoenergetic spin states. The [Rh₂C₃]⁺ ion reacts with CH₄ at room temperature to form [Rh₂C]⁺ + C₃H₄ and [Rh₂C₂H₂]⁺ + C₂H₂ as the major products. In addition to the [Rh₂C]⁺ ion, the [Rh₂ ¹³C]⁺ ion is formed at about one-half of the [Rh₂C]⁺ intensity when the isotopic-labeled ¹³CH₄ sample is used. The production of [Rh₂ ¹³C]⁺ indicates that the linear C₃ moiety of [Rh₂C₃]⁺ can be replaced by the bare carbon atom of methane with all four C-H bonds being activated. The calculations suggest that the overall reactions are thermodynamically exothermic, and that the two Rh centers are the reactive sites for C-H bond activation and hydrogen atom transfer reactions.

SUBMITTER: Wu H 

PROVIDER: S-EPMC8549038 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature