Isolation and characterization of a californium metallocene

Californium (Cf) is currently the heaviest element accessible above microgram quantities. Cf isotopes impose severe experimental challenges due to their scarcity and radiological hazards. Consequently, chemical secrets ranging from the accessibility of 5f/6d valence orbitals to engage in bonding, the role of spin-orbit coupling in electronic structure, and reactivity patterns compared to other f elements, remain locked. Organometallic molecules were foundational in elucidating periodicity and bonding trends across the periodic table(1-3), with a twenty-first-century renaissance of organometallic thorium (Th) through plutonium (Pu) chemistry(4-12), and to a smaller extent americium (Am)(13), transforming chemical understanding. Yet, analogous curium (Cm) to Cf chemistry has lain dormant since the 1970s. Here, we revive air-/moisture-sensitive Cf chemistry through the synthesis and characterization of [Cf(C5Me4H)(2)Cl2K(OEt2)](n) from two milligrams of Cf-249. This bent metallocene motif, not previously structurally authenticated beyond uranium (U)(14,15), contains the first crystallographically characterized Cf-C bond. Analysis suggests the Cf-C bond is largely ionic with a small covalent contribution. Lowered Cf 5f orbital energy versus dysprosium (Dy) 4f in the colourless, isoelectronic and isostructural [Dy(C5Me4H)(2)Cl2K(OEt2)](n) results in an orange Cf compound, contrasting with the light-green colour typically associated with Cf compounds(16-22). Chemical experiments on californium are stymied by isotope availability and radioactivity considerations, but are advanced here with synthesis and characterization of an organometallic complex.

Automated summary

This study revives air-/moisture-sensitive Californium chemistry through the synthesis and characterization of an organometallic complex, providing new insights into Californium chemistry with its unique structural features.