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Tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) is ubiquitously used as a source of soluble Pd species for catalysis and as a precursor in the synthesis of more complex Pd structures. In spite of the massive usage of this convenient Pd complex, its nature in solution has not been revealed in detail and the applications rely on the assumed state and purity of the compound. In the present study we have developed a convenient NMR procedure to reveal the nature of Pd2(dba)3 and to determine the purity of the complex. Surprisingly, it was found that commercially available samples of Pd2(dba)3 may readily contain up to 40% of Pd nanoparticles in a wide range of sizes (10-200 nm). The study has shown that the routinely accepted practice of utilization of Pd2(dba)3 without analysis of the purity (both commercially available and prepared by common procedures) can introduce significant errors in the estimation of catalyst efficiency and lead to incorrect values of TON, TOF, and reported mol % values in the catalytic procedures. The presence of Pd nanoparticles in the catalyst precursor provides an opportunity for heterogeneous catalytic systems of different nature to be directly accessible from Pd2(dba) 3. In the present study we report a modified procedure for the synthesis of Pd2(dba)3?CHCl3 with 99% purity.
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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate