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• W2089066891 abstract "The complexes [Pd(3,5-C6Cl2F3)2L2] and [Pd(C6F5)2L2] (L = SC4H8 (tht), or SMe2) react in CCl3D to give a mixture also containing the heteroaryl products [Pd(3,5-C6Cl2F3)(C6F5)L2], whereas for L = PPh3, AsPh3, 2-picoline, 4-picoline, or 1/2COD, this exchange is not observed. The 19F NMR kinetic study supports that the scrambling of the aryl groups takes place with retention of configuration at both Pd centers via a triply-bridged binuclear activated complex [L(C6Cl2F3)Pd(μ-C6Cl2F3)(μ-C6F5)(μ-L)Pd(C6F5)L]⧧. The aryl double bridge is supported by a bridging S-donor ligand facilitating an otherwise difficult exchange (not observed for other weak L ligands, such as picolines, lacking a second lone pair). This constitutes the first reported example of reversible migration of σ-C-bonded groups between bis-organo Pd(II) complexes proceeding without cis−trans isomerization. The isomerization process is also observed, occurring at a much slower rate." @default.
• W2089066891 created "2016-06-24" @default.
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• W2089066891 date "1997-12-01" @default.
• W2089066891 modified "2023-10-16" @default.
• W2089066891 title "An Aryl Exchange Reaction with Full Retention of Configuration of the Complexes: Mechanism of the Aryl Exchange between [PdR₂L₂] Complexes in Chloroform (R = Pentahalophenyl, L = Thioether)" @default.
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• W2089066891 doi "https://doi.org/10.1021/om970721f" @default.
• W2089066891 hasPublicationYear "1997" @default.
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