Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Abstract Well‐characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPO q ) 2 (NO 3 )(py) (DOPO q =2,4,6,8‐tetra‐ tert ‐butyl‐1‐oxo‐1 H ‐phenoxazin‐9‐olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α‐radiolysis‐induced reaction of pyridine and/or the ligand. Computational analysis of the electronic structure of the complex reveals that the Cf III –ligand interactions are largely ionic.