Formation and coordination modes of the C4E4 moiety (E = COOMe) bound to two palladium(II) moieties.
Formation and coordination modes of the C4E4 moiety (E = COOMe) bound to two palladium(II) moieties.
复制标题
与两个钯 (II) 部分结合的 C4E4 部分 (E = COOMe) 的形成和配位模式。
作者：
Tetsuro Murahashi;Taketoshi Okuno;Kenta Usui;K. Takase;T. Otani;S. Ogoshi;H. Kurosawa
钯环戊二烯配合物 Pd{C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy) 与双阳离子 Pd(II) 配合物 [Pd(bipy)(CH(3)CN)(2)][BF(4)](2) 发生金属交换，得到末端 σ-钯化二烯配合物[Pd(2){μ-η(1):η(1)-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)(2)(CH(3)CN)(2)][BF(4)](2)。 X射线晶体分析表明，用PPh(3)配体取代末端σ-钯二烯配合物中的乙腈配体，导致σ-钯二烯部分的构象从倾斜的顺式变为平面的顺式。用乙腈中的二甲氧基乙炔二羧酸酯 (DMAD)（1 当量）处理双三苯基膦二钯络合物 [Pd(2)(PPh(3))(2)(CH(3)CN)(4)][PF(6)](2)，导致 DMAD 插入到 Pd-Pd 键上，得到[Pd(2){μ-η(1):η(1)-C(COOMe)C(COOMe)}(PPh(3))(2)(CH(3)CN)(4)][PF(6)](2)。添加第二个DMAD得到叶立德型配合物[Pd(2){μ-η(2):η(3)-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh(3))}(PPh(3))(2)(CH(3)CN)(3)][PF(6)](2)，其结构通过X射线晶体学分析确定。
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.) in acetonitrile resulted in the insertion of DMAD to the Pd-Pd bond to afford [Pd(2){μ-η(1):η(1)-C(COOMe)C(COOMe)}(PPh(3))(2)(CH(3)CN)(4)][PF(6)](2). Addition of the second DMAD gave the ylide-type complex [Pd(2){μ-η(2):η(3)-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh(3))}(PPh(3))(2)(CH(3)CN)(3)][PF(6)](2) of which the structure was determined by X-ray crystallographic analysis.