Polyvalent s-block elements: A missing link challenges the periodic law of chemistry for the heavy elements.

The Periodic Law of Chemistry is one of the great discoveries in cultural history. Elements behaving chemically similar are empirically merged in groups of a Periodic Table, each element with valence electrons per neutral atom, and with upper limit for the oxidation and valence numbers. Here, we report that among the usually mono- or di-valent s-block elements ( = 1 or 2), the heaviest members (Fr, Ra, E, and E) with atomic numbers Z = 87, 88, 119, 120 form unusual 5- or 6-valent compounds at ambient conditions. Together with well-reported basic changes of valence at the end of the 6d-series, in the whole 7p-series, and for 5g6f-elements, it indicates that at the bottom of common Periodic Tables, the classic Periodic Law is not as straightforward as commonly expected. Specifically, we predict the feasible experimental synthesis of polyvalent [RaL] ( = 4, 6) compounds.