Send to:

Choose Destination
See comment in PubMed Commons below
Dalton Trans. 2011 Nov 14;40(42):11080-8. doi: 10.1039/c1dt10692a. Epub 2011 Aug 15.

Reductive coupling of carbon monoxide by U(III) complexes--a computational study.

Author information

  • 1Department of Chemistry, Oxford University, Inorganic Chemistry Laboratory, South Parks Road, Oxford, UK OX1 3QR.


The role of U((η-C(8)H(6){Si(i)Pr(3)-1,4}(2))(η-C(5)Me(5)) and U((η-C(8)H(6){Si(i)Pr(3)-1,4}(2))(η-C(5)Me(4)H) in the reductive di- tri- and tetramerization of CO has been modelled using density functional methods and U(C(8)H(8))(C(5)H(5)) as the metal fragment. The orbital structure of U(C(8)H(8))(C(5)H(5)) is described. CO binding to form a monocarbonyl U(C(8)H(8))(C(5)H(5))(CO) is found, by a variety of methods, to place spin density on the CO ligand via back-bonding from the U5f orbitals. A possible pathway for formation of the yne diolate complex [U(C(8)H(8))(C(5)H(5))](2)C(2)O(2) is proposed which involves dimerization of U(C(8)H(8))(C(5)H(5))CO via coordination of the CO O atoms to the opposing U atoms followed by C-C bond formation to form a zig-zag intermediate, stable at low temperatures. The intermediate then unfolds to form the yne diolate. The structures of [U(C(8)H(8))(C(5)H(5))]C(2)O(2), the deltate complex [U(C(8)H(8))(C(5)H(5))]C(3)O(3) and the squarate complex [U(C(8)H(8))(C(5)H(5))]C(4)O(4) are optimized and provide good models for the experimental compounds. The reaction of further CO with a zig-zag intermediate to form deltate and squarate complexes was explored using Th(C(8)H(8))(C(5)H(5)) as a model and low energy pathways are proposed.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for Royal Society of Chemistry
    Loading ...
    Write to the Help Desk