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Silyl-Phosphino-Carbene Complexes of Uranium(IV)

Lookup NU author(s): Dr Erli Lu, Dr Stephen Liddle

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


Abstract

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Unprecedented silyl-phosphino-carbene complexes of uranium(IV) are presented, where before all covalent actinide–carbon double bonds were stabilised by phosphorus(V) substituents or restricted to matrix isolation experiments. Conversion of [U(BIPMTMS)(Cl)(μ-Cl)2Li(THF)2] (1, BIPMTMS=C(PPh2NSiMe3)2) into [U(BIPMTMS)(Cl){CH(Ph)(SiMe3)}] (2), and addition of [Li{CH(SiMe3)(PPh2)}(THF)]/Me2NCH2CH2NMe2 (TMEDA) gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(μ-Cl)Li(TMEDA)(μ-TMEDA)0.5]2 (3) by α-hydrogen abstraction. Addition of 2,2,2-cryptand or two equivalents of 4-N,N-dimethylaminopyridine (DMAP) to 3 gave [U{C(SiMe3)(PPh2)}(BIPMTMS)(Cl)][Li(2,2,2-cryptand)] (4) or [U{C(SiMe3)(PPh2)}(BIPMTMS)(DMAP)2] (5). The characterisation data for 3–5 suggest that whilst there is evidence for 3-centre P−C−U π-bonding character, the U=C double bond component is dominant in each case. These U=C bonds are the closest to a true uranium alkylidene yet outside of matrix isolation experiments.


Publication metadata

Author(s): Lu E, Boronski JT, Gregson M, Wooles AJ, Liddle ST

Publication type: Article

Publication status: Published

Journal: Angewandte Chemie International Edition

Year: 2018

Volume: 57

Issue: 19

Pages: 5506-5511

Print publication date: 04/05/2018

Online publication date: 13/03/2018

Acceptance date: 08/03/2018

Date deposited: 02/10/2019

ISSN (print): 1433-7851

ISSN (electronic): 1521-3773

Publisher: Wiley - VCH Verlag

URL: https://doi.org/10.1002/anie.201802080

DOI: 10.1002/anie.201802080

PubMed id: 29534326


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