Mechanistic studies on the reductive cyclooligomerisation of CO by U(III) mixed sandwich complexes; the molecular structure of [(U(eta-C8H6{Si(i)Pr3-1,4}2)(eta-Cp*)]2(mu-eta1:eta1-C2O2)

Alistair S Frey; F Geoffrey N Cloke; Peter B Hitchcock; Iain J Day; Jennifer C Green; Georgina Aitken

doi:10.1021/ja8059792

Mechanistic studies on the reductive cyclooligomerisation of CO by U(III) mixed sandwich complexes; the molecular structure of [(U(eta-C8H6{Si(i)Pr3-1,4}2)(eta-Cp*)]2(mu-eta1:eta1-C2O2)

J Am Chem Soc. 2008 Oct 22;130(42):13816-7. doi: 10.1021/ja8059792. Epub 2008 Sep 26.

Authors

Alistair S Frey¹, F Geoffrey N Cloke, Peter B Hitchcock, Iain J Day, Jennifer C Green, Georgina Aitken

Affiliation

¹ The Department of Chemistry and Biochemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QJ, UK.

PMID: 18817397
DOI: 10.1021/ja8059792

Abstract

The stoichiometric reaction of 1 equiv of CO with [(U(eta-C8H6{SiiPr3-1,4}2)(eta-Cp*)] affords the linear diuranium ynediolate complex [(U(eta-C8H6{SiiPr3-1,4}2)(eta-Cp*)]2(mu-eta1:eta1-C2O2) which does not react with further CO to give the deltate derivative [(U(eta-C8H6{SiiPr3-1,4}2)(eta-Cp*)]2(mu-eta1:eta2-C3O3). Spectroscopic and computational studies suggest a plausible mechanism for the formation of the deltate complex, in which a "zig-zag" diuranium ynediolate species is the key intermediate.