Synthesis and solution behavior of the trinuclear palladium(II) unsaturated carboxylate complexes triangle-Pd3[μ-O2CC(R′) = CHMe]6 (R′ = Me, H): X-ray structure of palladium(II) tiglate (R′ = Me)

The first examples of binary palladium(II) derivatives of unsaturated carboxylic acids are reported. It was found that the interaction of Pd₃(μ-OAc)₆ with the ,β-unsaturated 1-methylcrotonic (tiglic) and crotonic acids leads to the corresponding carboxylates of composition Pd₃μ-O₂CC(R′) = CHMe]₆, where R′ = Me (1) or H (2). The new compounds have been characterized by elemental analysis, solid and solution IR, ¹H and ¹³C NMR, and ESI mass spectrometry. The crystal structure of 1 has been determined. This molecule displays a central Pd₃ cyclic core with Pd–Pd distances of 3.093–3.171 Å. Each Pd–Pd bond is bridged by a pair of carboxylate ligands, one above and the other below the Pd₃ plane, providing a square planar coordination for each Pd atom in an approximate D_3h overall symmetry arrangement. Solution spectroscopic data show that the bridging η¹:η¹:μ₂ interaction of the carboxylates of 1 and 2 is readily displaced, with a change of the ligand to the terminal (η¹) coordination mode.