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Uranium Metalla-Allenes with Carbene Imido R₂C=U^IV=NR’ Units (R=Ph₂PNSiMe₃; R’=CPh₃): Alkali-Metal-Mediated Push–Pull Effects with an Amido Auxiliary

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

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Abstract

© 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.

Publication metadata

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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