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

doi:10.1039/c8sc01127c

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

Authors

Nikolaos Tsoureas

Jennifer C. Green

F. Geoffrey N. Cloke

Dr Horst Puschmann horst.puschmann@durham.ac.uk
Professor In Practice

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