The mercury test is a rapid and widely used method for distinguishing truly homogeneous molecular catalysis from nanoparticle metal catalysis. In the current work, using various M 0 and M II complexes of palladium and platinum that are often used in homogeneous catalysis as examples, we demonstrated that the mercury test is generally inadequate as a method for distinguishing between homogeneous and cluster/nanoparticle catalysis mechanisms for the following reasons: (i) the general and facile reactivity of both molecular M 0 and M II complexes toward metallic mercury and (ii) the very high and often unpredictable dependence of the test results on the operational conditions and the inability to develop universal quantitatively defined operational parameters. Two main types or mercury-induced transformations, the cleavage of M 0 complexes and the oxidative−reductive transmetalation of M II complexes, including a reaction of highly popular M II /NHC complexes, were elucidated using NMR, ESI-MS, and EDXRF techniques. A mechanistic picture of the reactions involving metal complexes was revealed with mercury, and representative metal species were isolated and characterized. Even in an attempt to not overstate the results, one must note that the use of the mercury tests often leads to inaccurate conclusions and complicates the mechanistic studies of these catalytic systems. As a general concept, distinguishing reaction mechanisms (homogeneous vs cluster/nanoparticle) by using catalyst poisoning requires careful rethinking in the case of dynamic catalytic systems.

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