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Uranium–Carbene–Imido Metalla-Allenes: Ancillary-Ligand-Controlled cis-/trans-Isomerisation and Assessment of trans Influence in the R₂C=U^IV=NR’ Unit (R=Ph₂PNSiMe₃; R’=CPh₃)

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

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Abstract

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Uranium(IV)–carbene–imido complexes [U(BIPMTMS)(NCPh3)(κ2-N,N’-BIPY)] (2; BIPMTMS=C(PPh2NSiMe3)2; BIPY=2,2-bipyridine) and [U(BIPMTMS)(NCPh3)(DMAP)2] (3; DMAP=4-dimethylamino-pyridine) that contain unprecedented, discrete R2C=U=NR’ units are reported. These complexes complete the family of E=U=E (E=CR2, NR, O) metalla-allenes with feasible first-row hetero-element combinations. Intriguingly, 2 and 3 contain cis- and trans-C=U=N units, respectively, representing rare examples of controllable cis/trans isomerisation in f-block chemistry. This work reveals a clear-cut example of the trans influence in a mid-valent uranium system, and thus a strong preference for the cis isomer, which is computed in a co-ligand-free truncated model—to isolate the electronic trans influence from steric contributions—to be more stable than the trans isomer by approximately 12 kJ mol−1with an isomerisation barrier of approximately 14 kJ mol−1.

Publication metadata

Author(s): Lu E, Cooper OJ, Tuna F, Wooles AJ, Kaltsoyannis N, Liddle ST

Publication type: Article

Publication status: Published

Journal: Chemistry - A European Journal

Year: 2016

Volume: 22

Issue: 33

Pages: 11559-11563

Print publication date: 08/08/2016

Online publication date: 13/07/2016

Acceptance date: 07/06/2016

ISSN (print): 0947-6539

ISSN (electronic): 1521-3765

Publisher: Wiley - VCH Verlag

URL: https://doi.org/10.1002/chem.201602690

DOI: 10.1002/chem.201602690

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