Abstract

AbstractThe blood‐red plutonocene complex Pu(1,3‐COT′′)(1,4‐COT′′) (4; COT′′=η8‐bis(trimethylsilyl)cyclooctatetraenyl) has been synthesized by oxidation of the anionic sandwich complex Li[Pu(1,4‐COT′′)2] (3) with anhydrous cobalt(II) chloride. The first crystal structure determination of an organoplutonium(IV) complex revealed an asymmetric sandwich structure for 4 where one COT′′ ring is 1,3‐substituted while the other retains the original 1,4‐substitution pattern. The electronic structure of 4 has been elucidated by a computational study, revealing a probable cause for the unexpected silyl group migration.

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