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Updated: Apr 22, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
DFT computations support the σ-complex assisted metathesis (σ-CAM) mechanism for the 1,4-Rh shift of
Yougui Li1, Gang He, Eric Assen B Kantchev
1School of Chemistry and Chemical Engineering, Hefei University of Technology, 193 Tunxi Road, Hefei 230009, Anhui, China. liyg@hfut.edu.cn ekantchev@hfut.edu.cn ekantchev@gmail.com.
Abstract:
DFT calculations support the σ-complex assisted metathesis (σ-CAM) mechanism recently proposed for the first 1,4-Rh shift of a Rh(III) complex rather than the oxidative addition/reductive elimination pathway characteristic of Rh(i). A single, concerted TS (ΔG(‡) = 27-34 kcal mol(-1)) was found and its electronic structure characterized by Bader's AIM analysis. The 4-centered TS is characterized by a enhanced charge separation (Rh and H atoms - positive, both C atoms - negative) relative to the σ-vinyl Rh starting material and the σ-aryl-Rh product. The AIM topological analysis of the electron density reveals a network of interactions: Rh with H as well as both Rh and H with both C(vinyl) and C(aryl) in the TS and confirms the C(vinyl)-Rh agnostic interaction observed experimentally in the σ-aryl-Rh product.
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