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

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