Oxidation of uranium(iv) thiocyanate complexes: cation-cation interactions in mixed-valent uranium coordination chains

Stefano Nuzzo; Jan van Leusen; Brendan Twamley; James A Platts; Paul Kögerler; Robert J Baker

doi:10.1039/c9dt01005j

Oxidation of uranium(iv) thiocyanate complexes: cation-cation interactions in mixed-valent uranium coordination chains

Dalton Trans. 2019 May 21;48(20):6704-6708. doi: 10.1039/c9dt01005j.

Authors

Stefano Nuzzo¹, Jan van Leusen, Brendan Twamley, James A Platts, Paul Kögerler, Robert J Baker

Affiliation

¹ School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland. bakerrj@tcd.ie.

PMID: 31041967
DOI: 10.1039/c9dt01005j

Abstract

Oxidation of Cs4[U(NCS)8] in MeCN or DMF affords structurally characterised examples of the mixed-valent UIV/VI compound Cs14[{U(NCS)8}3{UO2(NCS)4(H2O)}]·4.5H2O, or the [UIV-UV-UIV][UVI] species [U(DMF)8(μ-O)U(NCS)5(μ-O)U(DMF)7(NCS)][UO2(NCS)5]. Vibrational and magnetism data support their oxidation state formulism, which is further corroborated by computational methodology.