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Uranium(VI) sulfilimine complexes: a new class of nitrogen analogues of the uranyl ion
V C Williams1, M Müller, M A Leech
1Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.
Abstract:
The compound tetraphenylphosphonium tetrachlorooxo-S,S-diphenylsulfiliminatouranium, [Ph4P][UOCl4(NSPh2)], has been prepared in high yield from [Ph4P][UOCl5] and [Ph2S=NSiMe3]. An X-ray structure of this compound shows that the uranium atom has a pseudooctahedral geometry with oxygen and nitrogen atoms in trans positions. The structure of the analogous phosphoriminato complex [Ph4P][UOCl4(NPPh3)] has been determined for comparison. Derivatization of the sulfide group shows that only a limited range of functionalization confers stability toward reduction. The emission spectrum of the first electronic excited state reveals a greatly reduced energy compared with that of the uranyl ion. This red shift in the transition is consistent with the weakening of the U-N bond relative to the U-O bond.
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