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

Cory J Windorff; Maria J Beltran-Leiva; Thomas E Albrecht-Schönzart; Zhuanling Bai; Cristian Celis-Barros; Conrad A P Goodwin; Zachary Huffman; Noah C McKinnon; Joseph M Sperling

doi:10.1039/d1dt03041h

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

Dalton Trans. 2021 Oct 26;50(41):14537-14541. doi: 10.1039/d1dt03041h.

Authors

Cory J Windorff^{1

2}, Maria J Beltran-Leiva¹, Thomas E Albrecht-Schönzart¹, Zhuanling Bai¹, Cristian Celis-Barros¹, Conrad A P Goodwin³, Zachary Huffman¹, Noah C McKinnon¹, Joseph M Sperling¹

Affiliations

¹ Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, RM. 118 DLC, Tallahassee, Florida 32306, USA. ccelisbarros@fsu.edu.
² Department of Chemistry and Biochemistry, New Mexico State University, MSC 3C, PO Box 3001, Las Cruces, NM 88003, USA. windorff@nmsu.edu.
³ Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA.

PMID: 34635890
DOI: 10.1039/d1dt03041h

Abstract

The interplay of bond strength and covalency are examined in AnO₂Cl₂(OPcy₃)₂ (An = Pu, U) complexes. 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O_yl interactions relative to the free gas phase (PuO₂)²⁺ ion.