Divergent uranium- versus phosphorus-based reduction of Me3SiN3 with steric modification of phosphido ligands. Issue 22 (27th May 2020)

• Record Type: Journal Article
• Authors: Ward, Robert J.; Rungthanaphatsophon, Pokpong; Rosal, Iker del; Kelley, Steven P.; Maron, Laurent; Walensky, Justin R.
• Is Part Of: Chemical science. Volume 11:Issue 22(2020)
• Page Start: 5830
• Page End: 5835
• Publication Date: 2020-05-27
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d0sc02261f
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : We describe an example of a two-electron metal- and ligand-based reduction of Me3 SiN3 using uranium(iv ) complexes with varying steric properties. With uranium-based reduction, a U(vi ) intermediate is isolated. Abstract : We describe an example of a two-electron metal- and ligand-based reduction of Me3 SiN3 using uranium(iv ) complexes with varying steric properties. Reaction of (C5 Me5 )2 U(CH3 )[P(SiMe3 )(Ph)] with Me3 SiN3 produces the imidophosphorane complex, (C5 Me5 )2 U(CH3 )[NP(SiMe3 )2 (Ph)] through oxidation of phosphorus. However, a similar reaction with a more sterically encumbering phosphido ligand, (C5 Me5 )2 U(CH3 )[P(SiMe3 )(Mes)] forms the U(iv ) complex, (C5 Me5 )2 U[ κ 2 -( N, N )–N(SiMe3 )P(Mes)N(SiMe3 )]. In probing the mechanism of this reaction, a U(vi ) bis(imido) complex, (C5 Me5 )2 U(NSiMe3 ){N[P(SiMe3 )(Mes)]} was isolated. DFT calculations show an intramolecular reductive cycloaddition reaction leads to the formation of the U(iv ) bis(amido)phosphane from the U(vi ) bis(imido) complex. This is a rare example of the isolation of a reaction intermediate in f element chemistry.