A Structurally Characterized Organometallic Plutonium(IV) Complex

Christos Apostolidis; Olaf Walter; Jochen Vogt; Phil Liebing; Laurent Maron; Frank T Edelmann

doi:10.1002/anie.201701858

A Structurally Characterized Organometallic Plutonium(IV) Complex

Angew Chem Int Ed Engl. 2017 Apr 24;56(18):5066-5070. doi: 10.1002/anie.201701858. Epub 2017 Mar 30.

Authors

Christos Apostolidis¹, Olaf Walter¹, Jochen Vogt², Phil Liebing², Laurent Maron³, Frank T Edelmann²

Affiliations

¹ European Commission, Joint Research Centre, Directorate G-Nuclear Safety and Security, P.O. Box 2340, 76125, Karlsruhe, Germany.
² Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, Universitätsplatz 2, 39106, Magdeburg, Germany.
³ Laboratoire de Physique et Chimie des Nanoobjets (LPCNO), Université de Toulouse/INSA/CNRS (UMR5215), 135 avenue de Rangueil, 31077, Toulouse cedex 4, France.

Abstract

The 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.

Keywords: X-ray crystallography; plutonium; sandwich complexes; silyl group migration.

Publication types

Research Support, Non-U.S. Gov't