Palladium(II)–rare-earth metal(III) paddlewheel carboxylate complexes: Easy total acetate to pivalate metathesis

Bis-paddlewheel heterobimetallic complexes in which palladium(II) is connected to the rare-earth metals(III) [Pd(μ-OOCMe)4Ln(OH2)(μ,η2-OOCMe)]2 × 2HOOCMe (Ln = Nd, Sm, Eu, Yb and Tm) by four acetate bridges were synthesised by the reaction of Pd3(μ-OOCMe)6 with the LnIII acetates. The tetraacetate-bridged complexes were unexpectedly found to be readily transformed by the stoichiometric amount of pivalic acid into the mono-paddlewheel tetrapivalate-bridged analogues in which the paddlewheel structure [Pd(μ-OOCR)4Ln] maintains as established by X-ray crystallography. The role of the intra- and intermolecular H-bonding in these complexes is discussed.

Bis-paddlewheel heterobimetallic PdII-LnIII complexes [Pd(μ-OOCMe)4Ln(OH2)(μ,η2-OOCMe)]2 × 2HOOCMe (Ln = Nd, Sm, Eu, Yb and Tm were synthesised by the reaction of Pd3(μ-OOCMe)6 with the LnIII acetates. The tetraacetate-bridged complexes are readily transformed into the mono-paddlewheel tetrapivalate-bridged analogues maintaining the [Pd(μ-OOCR)4Ln] paddlewheel structure with the intra- and intermolecular H-bonding.Figure optionsDownload as PowerPoint slide