Synthesis and Reduction of Uranium(V) Imido Complexes with Redox‐Active Substituents. Issue 24 (6th April 2017)

• Record Type: Journal Article
• Authors: Mullane, Kimberly C.; Carroll, Patrick J.; Schelter, Eric J.
• Is Part Of: Chemistry. Volume 23:Issue 24(2017)
• Page Start: 5748
• Page End: 5757
• Publication Date: 2017-04-06
• Subjects: electrochemistry -- electronic structure -- imido -- redox chemistry -- uranium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201605758
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Organic azides that contain naphthyl functional groups were used to prepare uranium(V) imido complexes U V [=NC(2‐naph)Ph2 ][N(SiMe3 )2 ]3 (2 ), U V [=NC(2‐naph)3 ][N(SiMe3 )2 ]3 (3 ), and U V [=N(2‐naph)][N(SiMe3 )2 ]3 (4 ), and their properties were compared with U V [=NCPh3 ][N(SiMe3 )2 ]3 (1 ). The electronic structures of these compounds were investigated by solution electrochemistry studies, which revealed accessible U V/VI, U IV/V, and naphthalene 0 /naphthalene −1 couples. The uranium(V) naphthylimido complexes were reduced by potassium graphite to yield their uranium(IV) congeners K[U IV [=NC(2‐naph)Ph2 ][N(SiMe3 )2 ]3 ] (2‐K ), K[U IV [=NC(2‐naph)3 ][N(SiMe3 )2 ]3 ] (3‐K ), and K[U IV [=N(2‐naph)][N(SiMe3 )2 ]3 ] (4‐K ). The electronic structure of the dianionic compounds were investigated by DFT calculations, and this revealed that the second reduction was ligand‐based, which opens the possibility of accomplishing multi‐electron redox chemistry by using a tailored multiply‐bonded ligand. Abstract : Redox activity of uranium imido complexes : Tailored, redox‐active multiply bonded ligands that bear naphthalene moieties are developed in the coordination chemistry of uranium.