Mechanistic Studies on the Reductive Cyclooligomerisation of CO by U(III) Mixed Sandwich Complexes; the Molecular Structure of [(U(η-C 8 H 6 {Si i Pr 3 -1,4} 2 )(η-Cp*)] 2 (μ-η 1 :η 1 -C 2 O 2 )

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Mechanistic Studies on the Reductive Cyclooligomerisation of CO by U(III) Mixed Sandwich Complexes; the Molecular Structure of [(U(η-C 8 H 6 {Si i Pr 3 -1,4} 2 )(η-Cp*)] 2 (μ-η 1 :η 1 -C 2 O 2 )

2008; American Chemical Society; Volume: 130; Issue: 42 Linguagem: Inglês

10.1021/ja8059792

ISSN

1943-2984

Autores

Alistair S. P. Frey, F. Geoffrey N. Cloke, Peter B. Hitchcock, Iain J. Day, Jennifer C. Green, G. Aitken,

Tópico(s)

CO2 Reduction Techniques and Catalysts

Resumo

The stoichiometric reaction of 1 equiv of CO with [(U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)] affords the linear diuranium ynediolate complex [(U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)]2(μ-η1:η1-C2O2) which does not react with further CO to give the deltate derivative [(U(η-C8H6{SiiPr3-1,4}2)(η-Cp*)]2(μ-η1:η2-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.

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Mechanistic Studies on the Reductive Cyclooligomerisation of CO by U(III) Mixed Sandwich Complexes; the Molecular Structure of [(U(η-C 8 H 6 {Si i Pr 3 -1,4} 2 )(η-Cp*)] 2 (μ-η 1 :η 1 -C 2 O 2 )