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      A Structurally Characterized Organometallic Plutonium(IV) Complex

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          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 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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          An organometallic sandwich lanthanide single-ion magnet with an unusual multiple relaxation mechanism.

          Matthew Jeletic, Po-Heng Lin, Jennifer J Le Roy … (2011)
          A dysprosium(III) sandwich complex, [Dy(III)(COT″)(2)Li(THF)(DME)], was synthesized using 1,4-bis(trimethylsilyl)cyclooctatetraenyl dianion (COT″). The complex behaves as a single-ion magnet and demonstrates unusual multiple relaxation modes. The observed relaxation pathways strongly depend on the applied static dc fields.
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            Covalency in AnCp4 (An = Th-Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses.

            Matthew J Tassell, Nikolas Kaltsoyannis (2010)
            The geometric and electronic structures of the title compounds are calculated with scalar relativistic, gradient-corrected density functional theory. The most stable geometry of ThCp(4) (Cp = eta(5)-C(5)H(5)) and UCp(4) is found to be pseudo-tetrahedral (S(4)), in agreement with experiment, and all the other AnCp(4) compounds have been studied in this point group. The metal-Cp centroid distances shorten by 0.06 A from ThCp(4) to NpCp(4), in accord with the actinide contraction, but lengthen again from PuCp(4) to CmCp(4). Examination of the valence molecular orbital structures reveals that the highest-lying Cp pi(2,3)-based orbitals split into three groups of pseudo-e, t(2) and t(1) symmetry. Above these levels come the predominantly metal-based 5f orbitals, which stabilise across the actinide series, such that in CmCp(4), the 5f manifold is at more negative energy than the Cp pi(2,3)-based levels. The stability of the Cm 5f orbitals leads to an intramolecular ligand-->metal charge transfer, generating a Cm(III) f(7) centre and increased Cm-Cp centroid distance. Mulliken population analysis shows metal d orbital participation in the e and t(2) Cp pi(2,3)-based orbitals, which gradually decreases across the actinide series. By contrast, metal 5f character is found in the t(1) levels, and this contribution increases four-fold from ThCp(4) to AmCp(4). Examination of the t(1) orbitals suggests that this f orbital involvement arises from a coincidental energy match of metal and ligand orbitals, and does not reflect genuinely increased covalency (in the sense of appreciable overlap between metal and ligand levels). Atoms-in-molecules analysis of the electron densities of the title compounds (together with a series of reference compounds: C(2)H(6), C(2)H(4), Cp(-), M(CO)(6) (M = Cr, Mo, W), AnF(3)CO (An = U, Am), FeCp(2), LaCp(3), LaCl(3) and AnCl(4) (An = Th, Cm)) indicates that the An-Cp bonding is very ionic, increasingly so as the actinide becomes heavier. Caution is urged when using early actinide/lanthanide comparisons as models for minor actinides/middle lanthanides.
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              Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp3 (An = Th-Cm; Cp = η(5)-C5H5).

              Ian Kirker, Nikolas Kaltsoyannis (2011)
              The title compounds are studied with scalar relativistic, gradient-corrected (PBE) and hybrid (PBE0) density functional theory. The metal-Cp centroid distances shorten from ThCp(3) to NpCp(3), but lengthen again from PuCp(3) to CmCp(3). Examination of the valence molecular orbital structures reveals that the highest-lying Cp π(2,3)-based orbitals transform as 1e + 2e + 1a(1) + 1a(2). Above these levels come the predominantly metal-based 5f orbitals, which stabilise across the actinide series such that in CmCp(3) the 5f manifold is at more negative energy than the Cp π(2,3)-based levels. Mulliken population analysis shows metal d orbital participation in the e symmetry Cp π(2,3)-based orbitals. Metal 5f character is found in the 1a(1) and 1a(2) levels, and this contribution increases significantly from ThCp(3) to AmCp(3). This is in agreement with the metal spin densities, which are enhanced above their formal value in NpCp(3), PuCp(3) and especially AmCp(3) with both PBE and PBE0. However, atoms-in-molecules analysis of the electron densities indicates that the An-Cp bonding is very ionic, increasingly so as the actinide becomes heavier. It is concluded that the large metal orbital contributions to the Cp π(2,3)-based levels, and enhanced metal spin densities toward the middle of the actinide series arise from a coincidental energy match of metal and ligand orbitals, and do not reflect genuinely increased covalency (in the sense of appreciable overlap between metal and ligand levels and a build up of electron density in the region between the actinide and carbon nuclei).
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                Author and article information

                Contributors
                Dr. Olaf Walter: olaf.walter@ec.europa.eu
                Dr. Jochen Vogt: jochen.vogt@ovgu.de
                Prof. Dr. Laurent Maron: laurent.maron@irsamc.ups-tlse.fr
                Prof. Dr. Frank T. Edelmann:
                ORCID: http://orcid.org/0000-0001-5209-0018
                frank.edelmann@ovgu.de
                Journal
                Journal ID (nlm-ta): Angew Chem Int Ed Engl
                Journal ID (iso-abbrev): Angew. Chem. Int. Ed. Engl
                Journal ID (doi): 10.1002/(ISSN)1521-3773
                Journal ID (publisher-id): ANIE
                Title: Angewandte Chemie (International Ed. in English)
                Publisher: John Wiley and Sons Inc. (Hoboken )
                ISSN (Print): 1433-7851
                ISSN (Electronic): 1521-3773
                Publication date (Electronic): 30 March 2017
                Publication date (Print): 24 April 2017
                Volume: 56
                Issue: 18 ( doiID: 10.1002/anie.v56.18 )
                Pages: 5066-5070
                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
                Author information
                http://orcid.org/0000-0001-5209-0018
                Article
                Publisher ID: ANIE201701858
                DOI: 10.1002/anie.201701858
                PMC ID: 5485009
                PubMed ID: 28371148
                SO-VID: d27d31fa-f914-4adc-915a-73a6e341a228
                Copyright © © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
                License:

                This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

                History
                Date received : 20 February 2017
                Page count
                Figures: 5, Tables: 0, References: 67, Pages: 5, Words: 0
                Categories
                Subject: Communication
                Subject: Communications
                Subject: Organoactinide Complexes | Hot Paper
                Custom metadata
                source-schema-version-number 2.0
                component-id anie201701858
                cover-date April 24, 2017
                details-of-publishers-convertor Converter:WILEY_ML3GV2_TO_NLMPMC version:5.1.2 mode:remove_FC converted:06.07.2017

                ScienceOpen disciplines: Chemistry
                Keywords: plutonium,sandwich complexes,silyl group migration,x-ray crystallography
                Data availability:
                ScienceOpen disciplines: Chemistry
                Keywords: plutonium, sandwich complexes, silyl group migration, x-ray crystallography

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