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- Title
Uranium Metalla-Allenes with Carbene Imido R<sub>2</sub>C=U<sup>IV</sup>=NR′ Units (R=Ph<sub>2</sub>PNSiMe<sub>3</sub>; R′=CPh<sub>3</sub>): Alkali-Metal-Mediated Push-Pull Effects with an Amido Auxiliary.
- Authors
Lu, Erli; Tuna, Floriana; Lewis, William; Kaltsoyannis, Nikolas; Liddle, Stephen T.
- 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.
- Subjects
URANIUM; ALLENE; GAS phase reactions; ALKALI metal compounds; LITHIUM
- Publication
Chemistry - A European Journal, 2016, Vol 22, Issue 33, p11554
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201602603