A Structurally Characterized Organometallic Plutonium(IV) Complex

Christos Apostolidis (1) , Olaf Walter (1) , Jochen Vogt (2) , Phil Liebing (2) , Laurent Maron (3) , Frank T. Edelmann (2)

1 Directorate for Nuclear Safety and Security [Karlsruhe, Germany]
2 OVGU - Otto-von-Guericke-Universität Magdeburg = Otto-von-Guericke University [Magdeburg]
3 LPCNO - Laboratoire de physique et chimie des nano-objets

The blood-red plutonocene complex Pu(1,3-COT `')(1,4-COT `') (4; COT `' = eta(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 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.

Mots clés: sandwich complexes; plutonium; silyl group migration; X-ray crystallography

Domaines: Physique [physics]; Chimie

Christos Apostolidis, Olaf Walter, Jochen Vogt, Phil Liebing, Laurent Maron, et al.. A Structurally Characterized Organometallic Plutonium(IV) Complex. Angewandte Chemie International Edition, 2017, 56 (18), pp.5066-5070. ⟨10.1002/anie.201701858⟩. ⟨hal-01961171⟩