Issue 22, 2018

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
09 三月 2018
Accepted
05 五月 2018
First published
08 五月 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 5008-5014

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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