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.
Stephen T. Liddle
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.
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|
|Peer Reviewed||Peer Reviewed|
|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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