Selective Manipulation of Well-Defined Trinuclear Pd(II)-Complexes

Several strategies are available to design well-defined multimetallic molecular entities bearing functional ligands. Substoichiometric exchange reactions in the coordination sphere of pre-existing multinuclear precursors are relatively underexploited in this context. Palladium(II) acetate is not a mononuclear compound in the solid state but rather exists as a trimer, i. e. [Pd₃(OAc)₆]. Although this material is ubiquitously used to synthesize mononuclear Pd species, it may principally also lend itself to selective exchange of some of the edge-sharing acetate units in its triangular motif, whilst keeping the overall multinuclear architecture intact. Strikingly, little is known about the controlled manipulation and substoichiometric substitution chemistry of this well-defined conglomerate. We herein conclusively demonstrate that, for the first time, the targeted exchange of two or four acetate units from the Pd₃(acetate)₆ platform is possible, thereby installing either one or two new tridentate ligands onto this trinuclear architecture. Follow-up exchange and substitution chemistry is available without disrupting the multimetallic nature of the core structure. New complexes 2-7 are all conclusively characterized using multinuclear NMR spectroscopy, UV-vis and IR spectroscopy as well as X-ray diffraction analysis.