Issue 29, 2019

Oxidation of uranium(iv) mixed imido–amido complexes with PhEEPh and to generate uranium(vi) bis(imido) dichalcogenolates, U(NR)2(EPh)2(L)2

Abstract

This work provides new routes for the conversion of U(IV) into U(VI) bis(imido) complexes and offers new information on the manner in which the U(VI) compounds form. Many compounds from the series described by the general formula U(NR)2(EPh)2(L)2 (R = 2,6-diisopropylphenyl, tert-butyl; E = S, Se, Te; L = py, EPh) were synthesized via oxidation of an in situ generated U(IV) amido–imido species with Ph2E2. This synthetic sequence provides a general route into bis(imido) U(VI) chalcogenolate complexes, circumventing the need to perform problematic salt metathesis reactions on U(VI) iodides. Investigation into the speciation of the U(IV) complexes that form prior to oxidation found a significant dependence on the identity of the ancillary ligands, with tBu2bpy forming the isolable imido–(bis)amido complex, U(NDipp)(NHDipp)2(tBu2bpy)2. Together, these data are consistent with the view that the bis(imido) U(VI) motif – much like the uranyl ion, UO22+ – is a thermodynamic sink into which simple ligand frameworks are unable to prevent uranium from falling when in the presence of a suitable retinue of imido proligands.

Graphical abstract: Oxidation of uranium(iv) mixed imido–amido complexes with PhEEPh and to generate uranium(vi) bis(imido) dichalcogenolates, U(NR)2(EPh)2(L)2

Supplementary files

Article information

Article type
Paper
Submitted
14 fev 2019
Accepted
23 apr 2019
First published
24 apr 2019

Dalton Trans., 2019,48, 10865-10873

Author version available

Oxidation of uranium(IV) mixed imido–amido complexes with PhEEPh and to generate uranium(VI) bis(imido) dichalcogenolates, U(NR)2(EPh)2(L)2

N. C. Tomson, N. H. Anderson, A. M. Tondreau, B. L. Scott and J. M. Boncella, Dalton Trans., 2019, 48, 10865 DOI: 10.1039/C9DT00680J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements