Uranium(VI)-ligand bonds have been shown to gain stability from a strong trans uranium-oxo multiple bond as part of an inverse trans influence (ITI). As part of our continuing studies of ITI stabilization in high valent uranium chemistry, we turned our attention to the synthesis of mono-imido complexes to explore their electronic structures with variable ligands trans to the imido group. A comparison of the UVI(=NSiMe3)X[N(SiMe3)2]3 (X = Cl, Br, O) complexes with the previously reported UVIOX[N(SiMe3)2]3 (X = Cl, Br, O) complexes suggested that the donor strength of trimethylsilyl ligand is comparable to the oxo ligand. Additionally, the facile reduction of the uranium(V) mono-imido complexes, UV(=NSiMe3)[N(SiMe3)2]3 and UV(=NCPh3)[N(SiMe3)2]3, with KC8 allowed for the synthesis of the uranium(IV) mono-imido derivatives, K[UIV(=NSiMe3)[N(SiMe3)2]3] and K[UIV(=NCPh3)[N(SiMe3)2]3] respectively. Last, the uranium(IV) complex, K[UIV(=NSiMe3)[N(SiMe3)2]3], was found to be reactive toward electrophiles, demonstrating N–C single bond formation.

Implications for strong inverse trans influence stabilization in the chemistry of uranium nitrogen multiple bonds

249th National Meeting (2015)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.