Ab initio MO study of the full catalytic cycle of olefin hydrogenation by the Wilkinson catalyst RhCl(PR3)3

Coordination of α,β-unsaturated aldehydes on d6 Ru and Rh complexes: A DFT study

“…After optimization, fragment 29 does not keep the SP geometry but evolves to a Yshaped geometry (symmetry C 2v ) with a HRhH angle of 64°. The same structure has been found by Morokuma et al [30]. A qualitative analysis based on EHT calculations [31] has shown that such a structure is favored over the SP one when a poor r-donor and good p-donor is trans to the acute angle, which is the case of Cl in 29.…”

Dihydrogen Complexes as Homogeneous Reduction Catalysts

“…Morokuma and co-workers 63 have studied in detail, with the ab initio MO method, the potential energy profile for the catalytic cycle of ethylene hydrogenation by the Wilkinson-type catalyst RhCl(PH 3 ) 2 . The features of this profile fully support the Halpern mechanism for the Wilkinson-type catalysts.…”

Rhodium‐catalysed hydrogenation of enamides with monodentate phosphorous ligands. A density functional theory study

“…The accepted mechanism for the rhodium‐catalysed hydrogenation of enamides, elaborated on the basis of extensive experimental5, 35–42 and theoretical30–34, 43–45 studies using bidentate diphosphine ligands, is shown in Scheme . In the first step the substrate chelates the rhodium ion to give a square planar complex, which can interact with molecular hydrogen to form a weakly bound ion‐induced dipole species IID.…”