Exploration of uranium-heteroatom multiple bonding, specifically the pnictogens, has been of interest for several years because of its ability to provide insight into covalency and f-orbital participation in actinide-ligand bonding. The recent synthesis of a bridge uranium(IV) nitride by our group, [Na(DME)3][(NR2)2U(�-N)(CH2SiMe2NR)U(NR2)2] (1 , R = SiMe3), and its subsequent conversion into a nitride substituted uranyl analogue, [Na(DME)3][(NR2)2(O)U(�-N)(CH2SiMe2NR)U(NR2)2] (2 ) spurred our interest in uranium(IV) nitrides as precursors to new uranyl analogues. In this regard, we have attempted to isolate nitride substituted uranyl analogues of the heavier chalcogens by reaction of 1  with chalcogen sources.  Interestingly, this has not yielded the expected terminal chacogenides but instead resulted in formation chalcogenate species, [Na(18-crown-6)][(NR2)2U(�-N)(E CH2SiMe2NR)U(NR2)2] (E= Se, 3 ; Te, 4 ), wherein the chacogen atom was inserted into the U-CH2 bond. In an effort to synthesize an N=U=N uranyl analogue complex 1  was reacted with 1-azidoadamatane, which resulted in formation of a uranium imido nitride species, [Na(DME)3][(NR2)2(NAd)U(�-N)(CH2SiMe2NR)U(NR2)2] (5 ). Our efforts to extend this chemistry to the heavier pnictogens will also be discussed.

Exploring the formation of pnictogen uranium multiple bonds

248th National Meeting (2014)

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