We are exploring the atom transfer chemistry of the well known U(III) amide complex U(NR2)3 (R = SiMe3, 1) with a variety of reagents, including azides, amine-N-oxides, phosphine sulphides (Ph3PS), and Wittig reagents (Ph3PCH2), in an attempt to form complexes possessing U=E multiple bonds.  For example, reaction of 1 with Ph3PCH2 results in formation of a U(III) adduct, namely U(NR2)3(H2CPPh3) (2), which can be isolated in excellent yield. Upon standing in solution, however, 2 slowly converts into the U(IV) carbene complex U(CHPPh3)(NR2)3 (3).  In the solid-state, complex 3 features a short uranium-carbon bond (U-C = 2.268(9) Ang.), indicative of a rare U=C interaction.  Our efforts to understand the mechanism of carbene formation and the reactivity of this functional group will also be described.

Synthesis of uranium ligand multiple bonds via oxidative atom transfer to U[N(SiMe3)2]3

241st National Meeting (2011)

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