期刊
CHEMICAL SCIENCE
卷 5, 期 2, 页码 841-846出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3sc52742e
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资金
- COST Action - EUFEN: European F-Element Network [CM1006]
- Agence Nationale de la Recherche [ANR-10-BLAN-0729]
- FCT (Portugal) [SFRH/BPD/74194/2010]
- Fundação para a Ciência e a Tecnologia [SFRH/BPD/74194/2010] Funding Source: FCT
The reaction of the tripodal tris-amido U(III) complex [U{(SiMe2NPh)(3)-tacn}] (tacn = 1,4,7-triazacyclononane), 1, with 0.0625 and 0.25 equiv. of elemental sulfur affords the sulfide-bridged U(IV) complex [{U((SiMe2NPh)(3)-tacn)}(2)(mu-S)], 2, and the terminal persulfide U(V) complex [U{(SiMe2NPh)(3)-tacn}(eta(2)-S-2)], 4, respectively, in good yield. Two different electronic structures, U(V) persulfide and U(IV) supersulfide, were computed for complex 4 at the DFT level. The results show that complex 4 is best described as a U(V) persulfide species with a significant sulfur contribution. X-ray, magnetism and electrochemistry data support this description. Complex 4 is the first example of a terminal U(V) persulfide and of a two-electron reduction of S-8 by a U(III) complex. Complex 4 behaves as a S-atom transfer agent when reacted with PPh3, affording the persulfide-bridged diuranium(IV) complex [{U((SiMe2NPh)(3)-tacn)}(2)(mu-eta(2):eta(2)-S-2)], 5, and S=PPh3.
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