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

Tsoureas, Nikolaos, Cloke, Geoff, Green, Jennifer, Puschmann, Horst, Roe, Mark and Tizzard, Graham (2018) Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system. Chemical Science, 22. pp. 5008-5014. ISSN 2041-6520

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Abstract

The reaction of the syn-bimetallic bis(pentalene)dititanium complex Ti2(μ:η5,η5-Pn†)2 (Pn† = C8H4(1,4-SiiPr3)2) 1 with carbon suboxide (O=C=C=C=O, C3O2) results in trimerisation of the latter and formation of the structurally characterised complex [{Ti2(μ:η5,η5-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:η5,η5-Pn†)2 (η2-C3O2)], as the first structurally authenticated complex of carbon suboxide.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Depositing User: Geoff Cloke
Date Deposited: 11 May 2018 09:58
Last Modified: 01 Jul 2019 12:01
URI: http://sro.sussex.ac.uk/id/eprint/75685

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Project NameSussex Project NumberFunderFunder Ref
Activation and Functionalisation of Carbon Dioxide by Low Valent Uranium ComplexesG1619EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/M023885/1