Theoretical Studies of the b-Hydrogen Elimination from p-Allyl Palladium Complexes

Masato OSHIMA* and Noriko INOUE

Department of Nanochemistry, Faculty of Engineering, Tokyo Polytechnic University
1583 Iiyama, Atsugi, Kanagawa 243-0297, Japan

(Received: November 21, 2008; Accepted for publication: April 23, 2009; Advance publication: June 2, 2009)

  To analyze the mechanism of the b-hydrogen elimination process of h3-1,1-dimethylallylpalladium compounds, we assumed the plausible intermediates and transition states for composing the possible pathways. Their geometry optimization, and vibrational frequencies and energy calculations were carried out with density functional theory (DFT) at the B3LYP level. The most suitable pathway was that in which the allylic ligand transformed from h3- to h1-allyl form having agnostic interaction between b-hydrogen and palladium atoms, and succeeding elimination of b-hydrogen gave 2-methyl-1,3-butadiene moiety with low activation energy (9.76 kcal/mol).

キーワード: Palladium complex, b-hydrogen elimination, b-elimination, DFT calculation

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