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RESEARCH PRODUCT

Cs3UP2S8, a Coordination Polymer Containing the Unprecedented [U=S]2+Sulfidouranium(2+) Moiety

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Although terminal chalcogeno ligands are well known for the group 5 and 6 transition metals, they are highly unusual for the oxophilic group 4 metals and unknown so far for the lanthanides or actinides. Cs3UP2S8, is the first actinide compound containing a terminal M=S group. It was synthesized by reacting uranium metal, Cs2S, S, and P2S5 in a 4:1:8:3 ratio at 700 °C in an eutectic LiCl/CsCl mixture. The crystal structure was determined by single-crystal X-ray diffraction techniques. Cs3UP2S8 crystallizes in the rhombohedral space group R [a = 15.5217(8) A; c = 35.132(2) A, V = 8305.0(8) A3, Z = 18]. The crystal structure is based on a tetrahedral network type, wherein the uranium atoms are coordinated by a unusual sulfido moiety and thiophosphate groups in a pseudo-tetrahedral fashion. The U=S distance of 2.635(3) A observed in the sulfide moiety is approx. 0.2 A shorter than the average U–S single bond length, indicating a double-bond type character.