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

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

Cory J. Windorff,

*^ab Maria J. Beltran-Leiva,

^a Thomas E. Albrecht-Schönzart,^a Zhuanling Bai,

^a Cristian Celis-Barros,*^a Conrad A. P. Goodwin,

‡^c Zachary Huffman,^a Noah C. McKinnon^a and Joseph M. Sperling^a

Author affiliations

* Corresponding authors

^a Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, RM. 118 DLC, Tallahassee, Florida 32306, USA
E-mail: ccelisbarros@fsu.edu

^b Department of Chemistry and Biochemistry, New Mexico State University, MSC 3C, PO Box 3001, Las Cruces, NM 88003, USA
E-mail: windorff@nmsu.edu

^c Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA

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 [triple bond, length as m-dash] O_yl interactions relative to the free gas phase (PuO₂)²⁺ ion.

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DOI: https://doi.org/10.1039/D1DT03041H
Article type: Communication
Submitted: 07 Sep 2021
Accepted: 01 Oct 2021
First published: 01 Oct 2021

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Dalton Trans., 2021,50, 14537-14541

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

C. J. Windorff, M. J. Beltran-Leiva, T. E. Albrecht-Schönzart, Z. Bai, C. Celis-Barros, C. A. P. Goodwin, Z. Huffman, N. C. McKinnon and J. M. Sperling, Dalton Trans., 2021, 50, 14537 DOI: 10.1039/D1DT03041H

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Dalton Transactions

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

Abstract

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

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