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Density Functional Computations for Co(I)‐Catalyzed Intermolecular Hydroacylation of Benzaldehydes
Author(s) -
Wang Fen,
Meng Qingxi
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201902097
Subject(s) - hydroacylation , benzaldehyde , reductive elimination , chemistry , decarbonylation , density functional theory , oxidative addition , intermolecular force , catalysis , medicinal chemistry , photochemistry , computational chemistry , aldehyde , organic chemistry , molecule
Density functional theory (DFT) was employed to study and expound Co(I)‐catalyzed intermolecular hydroacylation of benzaldehydes. The ωB97XD/6‐31G(d,p) level (LANL2DZ(f) for I and Co) was applied to optimize all intermediates and transition states. The computational results revealed that Co(I)‐catalyzed hydroacylation went primarily through the oxidative addition, hydrogen migration, and reductive elimination, the rate‐limiting step was the reductive elimination, and the ester was dominating product. The complexation of benzaldehyde occurred prior to its oxidative addition in the active three‐coordinated cobalt‐diphosphine‐benzaldehyde intermediate. The decarbonylation would be prohibited as a result of high relative Gibbs free energies. Moreover, the role of iodide ion, the additive i Pr 2 NEt, and the solvent toluene were studied in detail.