title: DFT computations support the σ-complex assisted metathesis (σ-CAM) mechanism for the 1,4-Rh shift of Cp*Rh(III)-(η(1)-β-styryl) complexes.
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.
authors.affiliation: School 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.
authors.forename: Yougui
authors.initials: Y
authors.lastname: Li
authors.forename: Gang
authors.initials: G
authors.lastname: He
authors.forename: Eric Assen B
authors.initials: EA
authors.lastname: Kantchev