Plutonium coordination and redox chemistry with the CyMe4-BTPhen polydentate N-donor extractant ligand

Sean D Reilly; Jing Su; Jason M Keith; Ping Yang; Enrique R Batista; Andrew J Gaunt; Laurence M Harwood; Michael J Hudson; Frank W Lewis; Brian L Scott; Clint A Sharrad; Daniel M Whittaker

doi:10.1039/c8cc06015k

Plutonium coordination and redox chemistry with the CyMe₄-BTPhen polydentate N-donor extractant ligand

Chem Commun (Camb). 2018 Nov 18;54(89):12582-12585. doi: 10.1039/c8cc06015k. Epub 2018 Oct 23.

Authors

Affiliations

¹ Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA. gaunt@lanl.gov.
² Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK.
³ Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK and Department of Applied Sciences, Faculty of Health and Life Sciences, Northumbria University, Newcastle upon Tyne, NE1 8ST, UK.
⁴ School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.

PMID: 30349920
DOI: 10.1039/c8cc06015k

Abstract

Complexation of Pu(iv) with the actinide extractant CyMe₄-BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline) was followed by vis-NIR spectroscopy in acetonitrile solution. The solid-state structure of the crystallized product suggests that Pu(iv) is reduced to Pu(iii) upon complexation. Analysis by DFT modeling is consistent with metal-based rather than ligand-based reduction.