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Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary

Lu, Erli; Tuna, Floriana; Lewis, William; Kaltsoyannis, Nikolas; Liddle, Stephen T.

Authors

Erli Lu

Floriana Tuna

William Lewis

Nikolas Kaltsoyannis

Stephen T. Liddle



Abstract

We 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=CR2 interactions, 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.

Citation

Lu, E., Tuna, F., Lewis, W., Kaltsoyannis, N., & Liddle, S. T. (2016). Uranium Metalla-Allenes with Carbene Imido R2C=UIV=NR′ Units (R=Ph2PNSiMe3; R′=CPh3): Alkali-Metal-Mediated push–pull effects with an Amido Auxiliary. Chemistry - A European Journal, 22(33), https://doi.org/10.1002/chem.201602603

Journal Article Type Article
Acceptance Date Jul 12, 2016
Online Publication Date Jul 12, 2016
Publication Date Aug 1, 2016
Deposit Date Sep 28, 2017
Publicly Available Date Sep 28, 2017
Journal Chemistry - A European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 22
Issue 33
DOI https://doi.org/10.1002/chem.201602603
Public URL https://nottingham-repository.worktribe.com/output/797814
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/chem.201602603/abstract
Additional Information This is the peer reviewed version of the following article: E.Lu, F.Tuna, W.Lewis, N.Kaltsoyannis, S.T. Liddle, Chem. Eur. J. 2016, 22, 11554, which has been published in final form at doi:10.1002/chem.201602603. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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