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Issue 22, 2018
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Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system

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Abstract

The reaction of the syn-bimetallic bis(pentalene)dititanium complex Ti2(μ:η55-Pn)2 (Pn = C8H4(1,4-SiiPr3)2) 1 with carbon suboxide (O[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]O, C3O2) results in trimerisation of the latter and formation of the structurally characterised complex [{Ti2(μ:η55-Pn)2}{μ-C9O6}]. The trimeric bridging C9O6 unit in the latter contains a 4-pyrone core, a key feature of both the hexamer and octamer of carbon suboxide which are formed in the body from trace amounts of C3O2 and are, for example, potent inhibitors of Na+/K+-ATP-ase. The mechanism of this reaction has been studied in detail by DFT computational studies, which also suggest that the reaction proceeds via the initial formation of a mono-adduct of 1 with C3O2. Indeed, the carefully controlled reaction of 1 with C3O2 affords [Ti2(μ:η55-Pn)22-C3O2)], as the first structurally authenticated complex of carbon suboxide.

Graphical abstract: Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system

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Publication details

The article was received on 09 Mar 2018, accepted on 05 May 2018 and first published on 08 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC01127C
Chem. Sci., 2018,9, 5008-5014
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system

    N. Tsoureas, J. C. Green, F. G. N. Cloke, H. Puschmann, S. M. Roe and G. Tizzard, Chem. Sci., 2018, 9, 5008
    DOI: 10.1039/C8SC01127C

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