Reactions of Allenes. IV. New Palladium Complexes Having a Bridged Allene Trimer Ligand

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概要

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• Di-μ-acetato-[2,2′-(1-methyleneethylene)bis-π-allyl]dipalladium (I) was obtained (18%) by the reaction of allene and palladium acetate. Its structure was estimated from the data of elemental analysis, molecular weight, hydrogenolysis reaction, IR, and NMR. Complex I was synthesized otherwise by the reaction of allene with di-μ-acetato-2,2′-bi-π-allyldipalladium. The insertion mechanism for the latter reaction was confirmed by the product of the reaction using allene-<I>d</I><SUB>4</SUB>, Pd<SUB>2</SUB>(C<SUB>9</SUB>H<SUB>8</SUB>D<SUB>4</SUB>)(CH<SUB>3</SUB>COO)<SUB>2</SUB>. It was found that this insertion reaction was by far faster than analogous reactions with bis(acetylacetonato)-2,2′-bi-π-allyldipalladium or di-μ-acetato-bis-(π-allyl palladium). The observed acceleration was assumed to be due to strain in the substrate. From NMR data of I and other π-allylpalladium complexes already published, it was shown that the difference in chemical shifts between <I>syn</I> and <I>anti</I> protons of π-allyl complexes is dependent on the substituents on the central carbon; the nonconjugated substituents give smaller values (0,9–1.01 ppm for μ-chloro complexes), and α,β-unsaturated substituents give larger values (1.27–1.28 ppm for μ-chloro complexes). Chloro and acetylacetonato derivatives of I, and the activation energy for spin exchange of saturated methylene protons in I are also described.

• 公益社団法人 日本化学会の論文

著者

• Okamoto Tadashi

  Institute For Chemical Research Kyoto University

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