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

Tsoureas, Nikolaos; Green, Jennifer C.; Cloke, F. Geoffrey N.; Puschmann, Horst; Roe, S. Mark; Tizzard, Graham

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


Authors

Nikolaos Tsoureas

Jennifer C. Green

F. Geoffrey N. Cloke

S. Mark Roe

Graham Tizzard



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[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: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.

Citation

Tsoureas, N., Green, J. C., Cloke, F. G. N., Puschmann, H., Roe, S. M., & Tizzard, G. (2018). Trimerisation of carbon suboxide at a di-titanium centre to form a pyrone ring system. Chemical Science, 9(22), 5008-5014. https://doi.org/10.1039/c8sc01127c

Journal Article Type Article
Acceptance Date May 5, 2018
Online Publication Date May 8, 2018
Publication Date Jun 14, 2018
Deposit Date Jun 27, 2018
Publicly Available Date Jun 27, 2018
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 9
Issue 22
Pages 5008-5014
DOI https://doi.org/10.1039/c8sc01127c
Public URL https://durham-repository.worktribe.com/output/1323376

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