Inorganic Chemistry
Communication
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addition or atom abstraction. For example, Meyer and co-
workers reported that [((AdArO)3N)U(DME)]2(μ-Se) reacts
with elemental Se to form [((AdArO)3N)U]2(μ-η2:η2-Se2)(μ-
DME),42 but the Se atom abstraction reaction was not
described. Similarly, Mazzanti and co-workers reported that
the uranium(V) disulfide [U((SiMe2NPh)3-tacn)(η2-S2)] reacts
with Ph3P to give Ph3PS, but the metal-containing
component of the reaction mixture proved to be intractable.17
In summary, we have demonstrated that elemental S and Se
react with the terminal sulfide complex 1 to generate new
terminal uranium(IV) dichalcogenide complexes, 2 and 5.
Importantly, this addition is reversible, and the reaction of the
dichalcogenides with a phosphine regenerates complex 1,
concomitant with the formation of R3PE (E = S, Se). This
reversibility suggests that 1 could be developed as a catalyst for
chalcogen-atom transfer, and we are currently exploring this
possibility.
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ASSOCIATED CONTENT
■
S
* Supporting Information
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1993, 32, 85−87.
Experimental procedures, crystallographic details (as a CIF
file), and spectral data for complexes 2−5. This material is
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́
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AUTHOR INFORMATION
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Corresponding Author
(31) Fedin, V. P.; Sokolov, M. N.; Fedorov, V. Y.; Yufit, D. S.;
Struchkov, Y. T. Inorg. Chim. Acta 1991, 179, 35−40.
(32) Mathur, P.; Sekar, P.; L. Rheingold, A.; Liable-Sands, L. M. J.
Chem. Soc., Dalton Trans. 1997, 2949−2954.
Notes
The authors declare no competing financial interest.
(33) Hernandez-Molina, R.; Sokolov, M.; Nunez, P.; Mederos, A. J.
Chem. Soc., Dalton Trans. 2002, 1072−1077.
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(35) Hu, J.; Zhuang, H.-H.; Liu, S.-X.; Huang, J.-L. Transition Met.
Chem. 1998, 23, 547−552.
ACKNOWLEDGMENTS
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This work was supported by the U.S. Department of Energy,
Office of Basic Energy Sciences, Chemical Sciences, Bio-
sciences, and Geosciences Division, under Contract DE-FG02-
09ER16067.
(36) Fedin, V. P.; Sokolov, M. N.; Virovets, A. V.; Podberezskaya, N.
V.; Fedorov, V. Y. Polyhedron 1992, 11, 2395−2398.
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(38) Baccolini, G.; Boga, C.; Mazzacurati, M. J. Org. Chem. 2005, 70,
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