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

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[κ ²-(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){[double bond, length as m-dash]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.