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Lookup NU author(s): Dr Erli Lu, Dr Stephen Liddle
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© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimWe report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPMTMS)(NCPh3)(NHCPh3)(M)] (BIPMTMS=C(PPh2NSiMe3)2; M=Li or K) that can be described as R2C=U=NR’ push–pull metalla-allene units, as organometallic counterparts of the well-known push–pull organic allenes. The solid-state structures reveal that the R2C=U=NR’ units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR’ and U=CR2interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push–pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=UIV=N units.
Author(s): Lu E, Tuna F, Lewis W, Kaltsoyannis N, Liddle ST
Publication type: Article
Publication status: Published
Journal: Chemistry - A European Journal
Year: 2016
Volume: 22
Issue: 33
Pages: 11554-11558
Print publication date: 08/08/2016
Online publication date: 12/07/2016
Acceptance date: 01/06/2016
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: Wiley - VCH Verlag
URL: https://doi.org/10.1002/chem.201602603
DOI: 10.1002/chem.201602603
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