Theoretical and Computational Chemistry

The Chemical Space from Which the Periodic System Arose



Mendeleev came across with his first attempt to a periodic system by classifying and ordering the known elements by 1869. Order and similarity were based on knowledge of chemical compounds, which gathered together constitute the chemical space by 1869. Despite its importance, very little is known about the size and diversity of this space and even less is known about its influence upon Mendeleev's periodic system. Here we show, by analysing 11.484 substances reported in the scientific literature up to 1869 and stored in Reaxys database, that 80\% of the space was accounted by 12 elements, oxygen and hydrogen being those with most compounds. We found that the space included more than 2,000 combinations of elements, of which 5\%, made of organogenic elements, gathered half of the substances of the space. By exploring the temporal report of compounds containing typical molecular fragments, we found that Meyer's and Mendeleev's available chemical space had a balance of organic, inorganic and organometallic compounds, which was, after 1830, drastically overpopulated by organic substances. The size and diversity of the space show that knowledge of organogenic elements sufficed to have a panoramic idea of the space. We determined similarities among the 60 elements known by 1869 taking into account the resemblance of their combinations and we found that Meyer's and Mendeleev's similarities for the chemical elements agree to a large extent with the similarities allowed by the chemical space.


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