A Structurally Characterized Organometallic Plutonium(IV) Complex. Issue 18 (30th March 2017)

• Record Type: Journal Article
• Authors: Apostolidis, Christos; Walter, Olaf; Vogt, Jochen; Liebing, Phil; Maron, Laurent; Edelmann, Frank T.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 18(2017)
• Page Start: 5066
• Page End: 5070
• Publication Date: 2017-03-30
• Subjects: plutonium -- sandwich complexes -- silyl group migration -- X-ray crystallography; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201701858
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The blood‐red plutonocene complex Pu(1, 3‐COT′′)(1, 4‐COT′′) (4 ; COT′′=η 8 ‐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 for4 where one COT′′ ring is 1, 3‐substituted while the other retains the original 1, 4‐substitution pattern. The electronic structure of4 has been elucidated by a computational study, revealing a probable cause for the unexpected silyl group migration. Abstract : The neutral plutonium(IV) sandwich complex Pu(1, 3‐COT′′)(1, 4‐COT′′) (COT′′=η 8 ‐bis(trimethylsilyl)cyclooctatetraenyl) was synthesized and characterized by single‐crystal X‐ray diffraction. The asymmetric sandwich structure contains one 1, 3‐ and one 1, 4‐substituted COT′′ ring. The electronic structure of the compound was elucidated computationally, revealing a likely cause for silyl group migration.