Vinyl−Vinyl Coupling on Late Transition Metals through C−C Reductive Elimination Mechanism. A Computational Study

Vinyl−Vinyl Coupling on Late Transition Metals through C−C Reductive Elimination Mechanism. A Computational Study Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2002, Volume: 124, Number: 11, Pages: 2839-2852 Pages count : 14 DOI: 10.1021/ja017476i

Authors

Ananikov Valentine P. ^1,2 , Musaev Djamaladdin G. ² , Morokuma Keiji ²

Affiliations

1	Contribution from the N. D. Zelinsky Institute of Organic Chemistry, RAS, Leninsky Prospect 47, Moscow 117913, Russia
2	Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322

A detailed density functional study was performed for the vinyl−vinyl reductive elimination reaction from bis-σ-vinyl complexes [M(CHCH2)2Xn]. It was shown that the activity of these complexes decreases in the following order: PdIV, PdII > PtIV, PtII, RhIII > IrIII, RuII, OsII. The effects of different ligands X were studied for both platinum and palladium complexes, which showed that activation barriers for C−C bond formation reaction decrease in the following order: X = Cl > Br, NH3 > I > PH3. Steric effects induced either by the ligands X or by substituents on the vinyl group were also examined. In addition, the major factors responsible for stereoselectivity control on the final product formation stage and possible involvement of asymmetric coupling pathways are reported. In all cases ΔE, ΔH, ΔG, and ΔGaq energy surfaces were calculated and analyzed. The solvent effect calculation shows that in a polar medium halogen complexes may undergo a reductive elimination reaction almost as easily as compounds with phosphine ligands.

Ananikov V.P. , Musaev D.G. , Morokuma K.
Vinyl−Vinyl Coupling on Late Transition Metals through C−C Reductive Elimination Mechanism. A Computational Study
Journal of the American Chemical Society. 2002. V.124. N11. P.2839-2852. DOI: 10.1021/ja017476i Scopus OpenAlex

Scopus:	2-s2.0-0037139496
OpenAlex:	W2089489360

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