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Updated: Oct 25, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Bis-Nitrene Prevails: Ligand-Controlled Divergence from the Conventional Mononitrene Pathway in Dirhodium Catalysis
Fenghui Lu1, Zhuofeng Ke2, Xinfang Xu3
1School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou510006, China.
Abstract:
Dirhodium paddlewheel complexes are widely used in C-H amination, yet whether bis-nitrene intermediates participate in catalysis remains an open question. Through systematic DFT calculations at the M06L/dgdzvp/SMD level, we show that both axial and bridging ligands exert strong control over the relative stability of mono-versus bis-nitrene species. Key to this control is π-backdonation from the Rh-Rh π orbital into the vacant p orbital of the nitrene, which stabilizes triplet intermediates and facilitates bis-nitrene formation. The electronic structures of mono- and bis-nitrenes differ in a fundamental way: spin density is distributed across the Rh-Rh-N framework in mononitrenes, whereas it becomes localized on individual Rh-N bonds in bis-nitrenes. These findings establish ligand-controlled spin-state modulation as a key determinant of intermediate speciation, providing new physical insights into dirhodium-catalyzed C-H amination.
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