DFT Computational Study of the Mechanism of Allyl Halides Carbonylation Catalyzed by Nickel Tetracarbonyl

• Published in: Journal of the American Chemical Society Vol. 125; no. 34; pp. 10412 - 10419
• Main Authors: Bottoni, Andrea, Miscione, Gian Pietro, Novoa, Juan J, Prat-Resina, Xavier
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 27.08.2003
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Catalytic reaction; Molecular structure; Reaction path; Theoretical study; Hartree Fock method; Transition metal Carbonyl Complexes; Complex catalyst; Energy barrier; Allylic compound; Carbonylation; Halogenated hydrocarbon; Transition state; Nickel Carbonyl Complexes; Density functional method
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja030100f

A theoretical investigation at the DFT(B3LYP) level on the carbonylation reaction of allyl bromide catalyzed by nickel tetra-carbonyl Ni(CO)4 is discussed. The computational results show the following:  (i) Three main steps characterize the catalytic cycle:  (a) an oxidative addition step, (b) a carbonylation step, and (c) a reductive elimination step where the acyl product is obtained and the catalyst is regenerated. (ii) Both Ni(CO)3 and Ni(CO)4 complexes can behave as “active” catalytic species. (iii) The oxidative addition leads to the formation of either η3 or η1-allyl nickel complexes, which are involved in a fast equilibrium. (iv) The carbonylation occurs much more easily on the η1 than on the η3 intermediates.