334912-05-9Relevant academic research and scientific papers
Syntheses of palladated aryldithioacetals. Unexpected rearrangement involving C-S and C-Pd bonds
Vicente, José,Abad, José-Antonio,Hernández-Mata, Francisco S.,Jones, Peter G.
, p. 1109 - 1114 (2008/10/08)
The reaction of C6HI(OMe)3-2,3,4- CH(STo)2-6 (1) (To = 4-tolyl) with [Pd(dba)2] (dba = dibezylideneacetone) at room temperature gives [Pd2{κ2-C,S-CH(STo)(C6H(STo-2) (OMe)3-3,4,5)2 (μ-I)2] (3) or, in the presence of Tl(OTf) (OTf = CF3SO3) and bpy (2,2′-bipyridine), the cationic cyclopalladated complex [Pd{κ2-C,S-C6H(OMe)3-2,3,4- CH(STo)2-6}(bpy)]OTf (2). 3 reacts with Tl(OTf) and (i) RNC (1:2:4) to give cis-[Pd{κ2-C,S-CH(STo){C6H(STo-2) (OMe)3-3,4,5}}-CNR)2]OTf [R = 2,6-dimethylphenyl (4), tBu (4′)] or (ii) bpy to give an isometric form of 2, cis-[Pd{κ2-C,S-CH(STo){C6H(STo-2)(OMe)3- 3,4,5}}(bpy)]OTf (5). The last reaction can be reversed by reacting 5 with NaI. The compound 2 reacts with NaI to give [Pd(C6H(OMe)3- 2,3,4-(CH(STo)2-6)I(bpy)] (6), which can be also prepared by reaction of 1 with [Pd(dba)2] in the presence of bpy. Complex 2 isomerizes to 5 when refluxed in 1,2-dichloroethane. The crystal structures of 2 and 4 have been determined by X-ray diffraction studies.
