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)

    Research output: Contribution to journalArticlepeer-review

    266 Downloads (Pure)

    Abstract

    We report 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-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 languageEnglish
    Pages (from-to) 11559–11563
    JournalChemistry - A European Journal
    Volume22
    Issue number33
    Early online date13 Jul 2016
    DOIs
    Publication statusPublished - 1 Aug 2016

    Fingerprint

    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.

    Cite this