Formation and coordination modes of the C4E4 moiety (E = COOMe) bound to two palladium(II) moieties.

The transmetallation of the palladacyclopentadiene complex Pd{C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy) with the dicationic Pd(II) complex [Pd(bipy)(CH(3)CN)(2)][BF(4)](2) afforded a terminally σ-palladated diene complex [Pd(2){μ-η(1):η(1)-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)(2)(CH(3)CN)(2)][BF(4)](2). It was revealed by X-ray crystallographic analysis that replacement of the acetonitrile ligands in a terminally σ-palladated diene complex with PPh(3) ligands resulted in the conformation change of the σ-palladated diene moiety from skewed s-cis to planar s-trans. Treatment of a bis-triphenylphosphine dipalladium complex [Pd(2)(PPh(3))(2)(CH(3)CN)(4)][PF(6)](2) with dimethoxyacetylene dicarboxylate (DMAD) (1 equiv.

Stereoretentive elimination and trans-olefination of the dicationic dipalladium moiety [Pd2Ln]2+ bound on 1,3,5-trienes.

The reaction of [Pd(2)(CH(3)CN)(6)][BF(4)](2) (1) with 1,3,5-hexatriene, 1,6-diphenyl-1,3,5-hexatriene (DPHT), or 2,2,9,9-tetramethyl-3,5,7-decatriene (DBHT) afforded bi-eta(3)-allyldipalladium complexes 3, 4, or 5. The reaction of 1 and DBHT proceeded in a stereospecific (syn) manner when the reaction was carried out in CD(2)Cl(2) under aerobic conditions, while a mixture of two diastereomers was formed under N(2) atmosphere. The two diastereomers (5-E,Z,E-antifacial and 5-E,E,E-antifacial) formed from DBHT were isolated, and the structure of 5-E,Z,E-antifacial, which was kinetically formed from the reaction of 1 and (E,E,E)-DBHT, was determined by X-ray diffraction analysis.