Browse by author
Lookup NU author(s): Dr Erli Lu, Dr Stephen Liddle
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 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.
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
Altmetrics provided by Altmetric