Electron-Reservoir Multiple Bond in RhC- for Dinitrogen Cleavage
Related Experiment Video
Updated: Oct 31, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Shi-Hu Du1, Jun Li1, Shi-Jun Wang1
1School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Abstract:
Multiple bonds involving the main-group element represent a prominent class of interactions whose formation and cleavage involve substantial electron redistribution, yet its functional role in redox processes remains unexplored. Herein, we identify a triple-bond character in the RhC- anion, which was generated in the gas phase and characterized spectroscopically by mass spectrometry and photoelectron spectroscopy. Concurrently, the RhC- species is demonstrated to exhibit dinitrogen cleavage capability. Quantum chemical calculations reveal that the resulting products feature a pronounced weakening of the Rh-C interaction along with concomitant C-N bond formation. Electronic structure analysis further indicates that the Rh-C triple bond acts as an electron reservoir, and nitrogen reduction proceeds primarily through cleavage of the Rh-C bond, which releases stored electrons. This work establishes the functional application of metal-carbon multiple bonds in dinitrogen cleavage, demonstrating their unique capacity to couple structural dynamics with redox chemistry and thereby establishing a transformative mechanism for designing electron-reservoir catalysts in dinitrogen activation and beyond.
Related Concept Videos
Radical Formation: Homolysis
¹H NMR: Complex Splitting
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations
Molecular Orbital Theory II
Radical Formation: Overview
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...
Resonance

