Abstract
[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-dimethylaminopyridine)
that contain unprecedented, discrete R2C=U=NR' units.
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-/transisomerisation
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 transinfluence
from steric contributions - to be more stable than the
trans-isomer by ~12 kJ mol-1 with an isomerisation barrier of ~14
kJ mol-1.
Original language | English |
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Pages (from-to) | 11559–11563 |
Journal | Chemistry - A European Journal |
Volume | 22 |
Issue number | 33 |
Early online date | 13 Jul 2016 |
DOIs | |
Publication status | Published - 1 Aug 2016 |
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Dive into the research topics of 'Uranium-Carbene-Imido Metalla-Allenes: Ancillary-Ligand-Controlled Cis-/Trans-Isomerisation and Assessment of Trans-Influence in the R2C=UIV=NR' Unit (R = Ph2PNSiMe3; R' = CPh3)'. Together they form a unique fingerprint.Datasets
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CCDC 1474824: Experimental Crystal Structure Determination
Lu, E. (Contributor), Cooper, O. J. (Contributor), Tuna, F. (Contributor), Wooles, A. (Contributor), Kaltsoyannis, N. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1lhnzq, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lhnzq&sid=DataCite
Dataset
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CCDC 1474823: Experimental Crystal Structure Determination
Lu, E. (Contributor), Cooper, O. J. (Contributor), Tuna, F. (Contributor), Wooles, A. (Contributor), Kaltsoyannis, N. (Contributor) & Liddle, S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2016
DOI: 10.5517/ccdc.csd.cc1lhnyp, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lhnyp&sid=DataCite
Dataset