Issue 42, 2011

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

Abstract

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

Supplementary files

Article information

Article type
Paper
Submitted
18 Apr 2011
Accepted
30 Jun 2011
First published
15 Aug 2011

Dalton Trans., 2011,40, 11080-11088

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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