Synthesis, characterization, and theoretical analysis of a plutonyl phosphine oxide complex

The synthesis of trans-PuO2Cl2(OPcy3)2, 1-Pu, has been carried out and confirmed by single crystal X-ray diffraction along with UV-vis-NIR, and 31P NMR spectroscopies. Theoretical analysis finds that despite a higher calculated covalency for the Pu–Cl interaction, the Pu–OPcy3 interaction is stronger due to the accumulation of electron density in the interatomic region. The coordination of equatorial ligands slightly decreases the strength of the Pu≡Oyl interactions relative to the free gas phase (PuO2)2+ ion.