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Issue 42, 2011
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Reductive coupling of carbon monoxide by U(III) complexes—a computational study

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The role of U((η-C8H6{SiiPr3-1,4}2)(η-C5Me5) and U((η-C8H6{SiiPr3-1,4}2)(η-C5Me4H) in the reductive di- tri- and tetramerization of CO has been modelled using density functional methods and U(C8H8)(C5H5) as the metal fragment. The orbital structure of U(C8H8)(C5H5) is described. CO binding to form a monocarbonyl U(C8H8)(C5H5)(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(C8H8)(C5H5)]2C2O2 is proposed which involves dimerization of U(C8H8)(C5H5)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(C8H8)(C5H5)]C2O2, the deltate complex [U(C8H8)(C5H5)]C3O3 and the squarate complex [U(C8H8)(C5H5)]C4O4 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(C8H8)(C5H5) as a model and low energy pathways are proposed.

Graphical abstract: Reductive coupling of carbon monoxide by U(iii) complexes—a computational study

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The article was received on 18 Apr 2011, accepted on 30 Jun 2011 and first published on 15 Aug 2011

Article type: Paper
DOI: 10.1039/C1DT10692A
Citation: Dalton Trans., 2011,40, 11080-11088
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    Reductive coupling of carbon monoxide by U(III) complexes—a computational study

    G. Aitken, N. Hazari, A. S. P. Frey, F. G. N. Cloke, O. Summerscales and J. C. Green, Dalton Trans., 2011, 40, 11080
    DOI: 10.1039/C1DT10692A

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