Divergent uranium- versus phosphorus-based reduction of Me3SiN3 with steric modification of phosphido ligands

Robert J. Ward; Pokpong Rungthanaphatsophon; Iker del Rosal; Steven P. Kelley; Laurent Maron; Justin R. Walensky

doi:10.1039/D0SC02261F

Divergent uranium- versus phosphorus-based reduction of Me₃SiN₃ with steric modification of phosphido ligands†

Robert J. Ward,^a Pokpong Rungthanaphatsophon,^a Iker del Rosal,^b Steven P. Kelley,

^a Laurent Maron

*^b and Justin R. Walensky

*^a

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* Corresponding authors

^a Department of Chemistry, University of Missouri, Columbia, MO, USA
E-mail: walenskyj@missouri.edu

^b Universite de Toulouse, CNRS, INSA, UPS, UMR, UMR 5215, LPCNO 135 Avenue de Ranguiel, 31077 Toulouse, France

Abstract

We describe an example of a two-electron metal- and ligand-based reduction of Me₃SiN₃ using uranium(IV) complexes with varying steric properties. Reaction of (C₅Me₅)₂U(CH₃)[P(SiMe₃)(Ph)] with Me₃SiN₃ produces the imidophosphorane complex, (C₅Me₅)₂U(CH₃)[N [double bond, length as m-dash] P(SiMe₃)₂(Ph)] through oxidation of phosphorus. However, a similar reaction with a more sterically encumbering phosphido ligand, (C₅Me₅)₂U(CH₃)[P(SiMe₃)(Mes)] forms the U(IV) complex, (C₅Me₅)₂U[κ²-(N,N)–N(SiMe₃)P(Mes)N(SiMe₃)]. In probing the mechanism of this reaction, a U(VI) bis(imido) complex, (C₅Me₅)₂U( [double bond, length as m-dash] 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.

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DOI: https://doi.org/10.1039/D0SC02261F
Article type: Edge Article
Submitted: 21 Apr 2020
Accepted: 20 May 2020
First published: 27 May 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2020,11, 5830-5835

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Divergent uranium- versus phosphorus-based reduction of Me₃SiN₃ with steric modification of phosphido ligands

R. J. Ward, P. Rungthanaphatsophon, I. D. Rosal, S. P. Kelley, L. Maron and J. R. Walensky, Chem. Sci., 2020, 11, 5830 DOI: 10.1039/D0SC02261F

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